Phosphorus-containing compositions and their use in hydrocyanation, isomerization and hydroformylation reactions

ABSTRACT

A polymeric, phosphorus-containing composition made by heating, in the presence of an initiator, preferably a free radical initiator, and optionally in the presence of one or more comonomers, at least one substituted phosphonylated 2,2′-dihydroxyl-1,1′-binaphthalene or at least one substituted 2,2′-dihydroxyl-1,1′-biphenylene.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to ethylenically unsaturated,phosphorus-containing, bidentate ligands (monomers) and polymericderivatives thereof as well as polymeric precursors to said polymericderivatives and methods of making the same. The present invention alsorelates to catalyst compositions involving a Group VIII metal in thepresence of the polymeric bidentate ligands and use of such catalysts inhydrocyanation, isomerization, and hydroformylation reactions.

[0003] 2. Description of the Related Art

[0004] Phosphorus-based ligands are generally known in catalysis,finding use for a number of commercially important chemicaltransformations. Phosphorus-based ligands commonly encountered incatalysis include phosphines, phosphinites, phosphonites and phosphites.Monodentate phosphorus ligands, e.g. monophosphine and monophosphiteligands, are compounds that usually contain a single phosphorus atomthat serves as an electron donor to a transition metal. Bidentatephosphorus ligands, e.g. bisphosphine, bisphosphinite, bisphosphonite,bisphosphite, and bis(phosphorus) ligands, in general, contain twophosphorus electron donor atoms and typically form cyclic chelatestructures with transition metals.

[0005] Two particularly important industrial processes using phosphorusligands as catalysts are olefin hydrocyanation and isomerization ofbranched nitriles to linear nitriles. Phosphite and phosphinite ligandsare particularly good ligands for both reactions. The hydrocyanation ofethylenically unsaturated compounds (olefins) using transition metalcomplexes with monodentate phosphite ligands is well documented in theprior art. See, for example, U.S. Pat. Nos. 3,496,215; 3,631,191;3,655,723; 3,766,237 and 5,543,536. Bidentate phosphite ligands havealso been shown to be particularly useful ligands in the hydrocyanationof activated ethylenically unsaturated compounds. See, for example, J.Chem. Soc., Chem. Commun., 1991, 1292; J.Chem. Soc., Chem. Commun.,1991, 803; PCT Pat. App. WO 9303839; U.S. Pat. Nos. 5,512,696;5,723,641; and 5,688,986. Bidentate phosphinite and phosphonite ligandsare described in U.S. Pat. Nos. 5,817,850; 5,523,453; 5,693,843; and PCTPat. App. WO 9964155, WO 9913983, WO 9946044, and WO 9843935.

[0006] Hydroformylation is another industrially useful process thatutilizes catalysts made from phosphorus-containing ligands. The use ofphosphine ligands, including diphosphines, is known for this purpose.The use of catalysts made from phosphite ligands is also known. Suchcatalysts usually contain a Group VIII metal, as described in, forexample, U.S. Pat. No. 5,235,113.

[0007] Recovery of the ligand and catalyst is important for a successfulcommercial process. Typical separation procedures to remove theproduct(s) from the catalyst and ligand involve extraction with animmiscible solvent or distillation. It is usually difficult to recoverthe catalyst and ligand quantitatively. For instance, distillation of avolatile product from a non-volatile catalyst results in thermaldegradation of the catalyst. Similarly, extraction results in some lossof catalyst into the product phase. For extraction, one would like to beable to select and/or control the solubility of the ligand and catalystto disfavor solubility in the product phase. These ligands and metalsare often very expensive and thus it is important to keep such losses toa minimum for a commercially viable process.

[0008] One method to solve the problem of catalyst and productseparation is to attach the catalyst to an insoluble support. Examplesof this approach have been previously described, and general referenceson this subject can be found in “Supported Metal Complexes: A NewGeneration of Catalysts”, F. R. Hartley and D. Boston, ReidelPublishing, 1985; Acta Polymer., 1996, 47, 1; “ComprehensiveOrganometallic Chemistry”, Ed: G. Wilkinson, F. G. A. Stone, and E. W.Abel, New York: Pergamon Press, 1982, Chapter 55, “Polymer SupportedCatalysts”; J. Mol. Catal. A, 1995, 104, 17; and Macromol. Symp., 1994,80, 241. Specifically, monophosphine and monophosphite ligands attachedto solid supports are described in these references. Bisphosphineligands have also been attached to solid supports and used forcatalysis, as described in, for example, U.S. Pat. Nos. 5,432,289 and5,990,318; J. Mol. Catal. A, 1996, 112, 217, J.Chem. Soc., Chem.Commun., 1996, 653; J. Org. Chem., 1998, 63, 3137; Spec. Chem., 1998,18, 224 and PCT Pat. App. WO 9812202. PCT Pat. Apps. WO 9906146 and WO9962855 show use of supported phosphorus ligands in hydrocyanation andhydroformylation reactions, respectively. Bisphosphite ligands have alsobeen grafted to solid supports such as those described in U.S. Pat. No.6,121,184. The solid support in these prior art examples can be organic,e.g., a polymer resin, or inorganic in nature.

[0009] Polymer-supported multidentate phosphorus ligands may be preparedby a variety of methods known in the art, as described in U.S. Pat. Nos.4,769,498 and 4,668,651, PCT Pat. App. WO 9303839 and WO 9906146, andEuropean Pat. Apps. EP 0864577 A2 and EP 0877029 A2. The prior artdiscloses side-chain polymers containing multidentate phosphorus ligandsas pendant groups.

[0010] Another method to solve the problem of separating the catalystfrom the reaction product is to copolymerize phosphorus-containingligands with other non-ligand monomers to produce insolublephosphorus-containing ligands. Examples of such polymer-immobilizedphosphine ligands have been reported in J. Am. Chem. Soc., 2000, 122,6217 and J. Org. Chem., 1986, 51, 4189. In addition, polymer-immobilizedphosphine-phosphite ligands and their use in hydroformylation catalysishave recently been described in Bull. Chem. Soc. Jpn., 1999, 72, 1911;J. Am. Chem. Soc., 1998, 120, 4051; and European Pat. App. EP 0864577.

[0011] To address the important issue of ligand recovery, this inventionprovides novel monomeric bidentate ligands and a method for theirsynthesis, polymeric bidentate ligands prepared from the monomericligands and a method for their synthesis, monomeric or polymericphosphorus-containing compositions that may be combined with a GroupVIII metal, and the use of this monomeric or polymericphosphorus-containing composition combined with a Group VIII metal toact as a catalyst in reactions for hydrocyanation, hydroformylation, andisomerization. The polymeric, phosporus-containing catalyst compositionis readily recoverable from the reaction products.

BRIEF SUMMARY OF THE INVENTION

[0012] In its first aspect, the present invention provides novel,phosphorus-containing bidentate ligand (monomer) compounds as shown inFormula I or as shown in Formula II, substituted with a vinyl groupand/or an acrylate group [e.g. ethenyl (CH₂═CH—), propenyl((CH₃)(H)C═CH—), acryloyl (CH₂═CH—C(O)—O—), or methacryloyl(CH₂═C(CH₃)—C(O)—O—)]:

[0013] wherein:

[0014] x=0 to 4;

[0015] y=0 to 2;

[0016] a and b individually are either 0, 1, or 2, provided a+b=2;

[0017] each Ar is individually phenyl or naphthyl, and the two Ar groupsthat are directly or indirectly (through an oxygen) bonded to the samephosphorus atom may be linked to each other by a linking unit selectedfrom the group consisting of direct bond, alkylidene, secondary ortertiary amine, oxygen, sulfide, sulfone, and sulfoxide;

[0018] each R is individually hydrogen, ethenyl, propenyl, acryloyl,methacryloyl, an organic radical with a terminal ethenyl, propenyl,acryloyl, or methacryloyl group, linear or branched alkyl, cycloalkyl,acetal, ketal, aryl, alkoxy, cycloalkoxy, aryloxy, formyl, ester,fluorine, chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl,hydrocarbylsulfonyl, hydrocarbylcarbonyl or cyclic ether;

[0019] each Ar can be further substituted with linear or branched alkyl,cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy, aryloxy, formyl,ester, fluorine, chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl,hydrocarbylsulfonyl, hydrocarbylcarbonyl or cyclic ether;

[0020] each R″ is individually hydrogen, ethenyl, propenyl, an organicradical with a terminal ethenyl or propenyl group, linear or branchedalkyl, cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy, aryloxy,formyl, ester, fluorine, chlorine, bromine, perhaloalkyl,hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarbylcarbonyl or cyclicether;

[0021] provided at least one R represents ethenyl, propenyl, acryloyl,methacryloyl or the organic radical with a terminal ethenyl, propenyl,acryloyl, or methacryloyl group or at least one R″ represents ethenyl,propenyl, or the organic radical with a terminal ethenyl or propenylgroup.

[0022] Preferred are compounds of Formula I wherein a=2, b=0, R isprimary or secondary alkyl located ortho to the oxygen bonded to Ar,wherein y≧1, and wherein at least one R″ is primary or secondary alkylgroup and is located at the ortho position of the oxygen bonded to thebinaphthalene group, or a compound of Formula II wherein a=2, b=0, R isprimary or secondary alkyl located ortho to the oxygen bonded to Ar,wherein x≧1 and wherein at least one R″ is primary or secondary alkylgroup and is located at the ortho positions of the oxygen bonded to thebiphenylene group.

[0023] In its second aspect, the invention is a process for preparingcertain phosphorus-containing bidentate ligand (monomer) compounds ofFormula I, wherein a is 1 or 2 and b is 0 or 1 with the condition thata+b=2, or certain compounds of Formula II, wherein a is 1 or 2 and b is0 or 1 with the condition that a+b=2. The process comprises:

[0024] (1) reacting at least one of acryloyl chloride or methacryloylchloride with a polyhydric alcohol to make at least one of monoacrylateor monomethacrylate,

[0025] (2) reacting at least one of the monoacrylate or monomethacrylatewith at least one of phosphorus trichloride or phosphorodichloridite oraryldichlorophosphine (Cl₂P—Ar) to give at least one ofphosphorochloridite- or aryl,aryloxychlorophosphinite-containingacrylate or methacrylate,

[0026] (3) reacting at least one of the phosphorochloridite- oraryl,aryloxychlorophosphinite-containing acrylate and/or methacrylatefrom step (2) with at least one compound of Formula III and/or at leastone compound of Formula IV,

[0027] wherein:

[0028] x=0 to 4;

[0029] y=0 to 2;

[0030] each R′ individually is hydrogen or M, wherein M is an alkalimetal or an alkaline earth metal,

[0031] each R″ is individually hydrogen, ethenyl, propenyl, an organicradical with a terminal ethenyl or propenyl group, linear or branchedalkyl, cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy, aryloxy,formyl, ester, fluorine, chlorine, bromine, perhaloalkyl,hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarbylcarbonyl or cyclicether.

[0032] Preferred are compounds of Formula III wherein a=2, b=0, R isprimary or secondary alkyl located ortho to the oxygen bonded to Ar,wherein y≧1, and wherein at least one R″ is primary or secondary alkylgroup and is located at the ortho position of the oxygen bonded to thebinaphthalene group, or a compound of Formula IV wherein a=2, b=0, R isprimary or secondary alkyl located ortho to the oxygen bonded to Ar,wherein x≧1 and wherein at least one R″ is primary or secondary alkylgroup and is located at the ortho positions of the oxygen bonded to thebiphenylene group.

[0033] In its third aspect, the present invention provides a method formaking a polymeric, phosphorus-containing composition by heating, in thepresence of an initiator, preferably a free radical initiator, andoptionally in the presence of a Group VIII metal, a compositioncomprising at least one compound of Formula I and/or at least onecompound of Formula II, provided at least one R represents ethenyl,propenyl, acryloyl, methacryloyl or the organic radical with a terminalethenyl, propenyl, acryloyl, or methacryloyl group or at least one R″represents ethenyl, propenyl, or the organic radical with a terminalethenyl or propenyl group.

[0034] In its fourth aspect, the present invention also provides apolymeric, phosphorus-containing composition made as described above inaspect three.

[0035] In its fifth aspect, the present invention also provides a methodfor producing a polymeric phosphorus-containing composition made by:

[0036] (1) heating in the presence of an initiator a compositioncomprising at least one compound of Formula III and/or at least onecompound of Formula IV,

[0037] wherein:

[0038] x=0 to 4;

[0039] y=0 to 2;

[0040] each R′ individually is hydrogen, an alkali metal, an alkalineearth metal or a hydroxyl-protective group selected from alkyl,alkoxyalkyl (e.g., CH₃OCH₂—), carbonylalkyl (e.g., CH₃—C(O)—), and acrown ether formed by taking both R′ groups together;

[0041] each R″ is individually hydrogen, ethenyl, propenyl, an organicradical with a terminal ethenyl or propenyl group, linear or branchedalkyl, cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy, aryloxy,formyl, ester, fluorine, chlorine, bromine, perhaloalkyl,hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarbylcarbonyl or cyclicether;

[0042] provided at least one R″ represents ethenyl, propenyl, or theorganic radical with a terminal ethenyl or propenyl group;

[0043] by contacting the composition with an initiator, preferably afree radical initiator, and heating to a preselected temperature for aperiod of time sufficient to permit reaction, and

[0044] (2) phosphonylating the resulting polymer.

[0045] Preferred are compounds of Formula III wherein a=2, b=0, R isprimary or secondary alkyl located ortho to the oxygen bonded to Ar,wherein y≧1, and wherein at least one R″ is primary or secondary alkylgroup and is located at the ortho position of the oxygen bonded to thebinaphthalene group, or a compound of Formula IV wherein a=2, b=0, R isprimary or secondary alkyl located ortho to the oxygen bonded to Ar,wherein x≧1 and wherein at least one R″ is primary or secondary alkylgroup and is located at the ortho positions of the oxygen bonded to thebiphenylene group.

[0046] In its sixth aspect, the present invention further provides apolymer composition made as described above in aspect five.

[0047] In its seventh aspect, the present invention further provides amethod to produce a polymeric, phosphorus-containing composition byheating a phosphorochloridite containing at least one acrylate or methylacrylate group in the presence of an initiator, preferably a freeradical initiator, to produce a polymer containing phosphorochloridite,and further reacting this polymer with at least one compound of FormulaIII and/or Formula IV wherein each R′ individually is H or M, with theprovision that if R′ is protected, the protecting group must be removedbefore reacting the compound of Formula III and/or Formula IV with thepolymer containing phosphorochloridite.

[0048] In its eighth aspect, the present invention further provides apolymer composition made as described above in aspect seven.

[0049] In its ninth aspect, the present invention further provides acatalyst composition comprising at least one monomeric,phosphorus-containing composition of aspect one and at least one GroupVIII metal, and/or at least one polymeric, phosphorus-containingcomposition of aspect four and/or aspect six and/or aspect eight and atleast one Group VIII metal, and/or at least one polymeric,phosphorus-containing, catalyst material of aspect three wherein thepolymerization was carried out in the presence of at least one GroupVIII metal.

[0050] In its tenth aspect, the present invention further provides theuse of any of the present catalyst compositions for a hydrocyanationprocess comprising reacting an unsaturated organic compound with HCN inthe presence of the catalyst composition, with or without a Lewis Acid.

[0051] In its eleventh aspect, the present invention further providesthe use of any of the present catalyst compositions for an isomerizationprocess comprising reacting an unsaturated organic nitrile compound inthe presence of the catalyst composition.

[0052] In its twelfth aspect, the present invention further provides theuse of any of the present catalyst compositions for a hydroformylationprocess comprising reacting an unsaturated organic compound with CO andH₂ in the presence of the catalyst composition.

DETAILED DESCRIPTION OF THE INVENTION

[0053] The phosphorus-containing compositions of the present inventionmay be viewed as belonging to the family of bidentate ligands, becauseeach pair of trivalent phosphorus atoms are potentially available tosimultaneously coordinately bond to a single Group VIII metal atom;i.e., the phosphorus atoms represent electron donors to the same metalatom of the resulting metal complex.

[0054] In each case, one of the phosphorus to oxygen bonds is associatedwith the oxygen of the hydroxyl group of a2,2′-dihydroxyl-1,1′-binaphthalene or 2,2′-dihydroxyl-1,1′-biphenylenestructure. The two other bonds associated with the trivalent phosphorusinvolve a pair of phosphorus to aryl carbon bonds, a pair of phosphorusto aryloxy oxygen bonds, or one phosphorus to aryl carbon bond and onephosphorus to aryloxy oxygen bond. Each aryl (Ar) or aryloxy (—O—Ar) maybe phenyl, naphthyl, substituted phenyl, or substituted naphthyl. Two Argroups that are directly or indirectly (through an oxygen) bonded to thesame phosphorus atom may be linked to each other by a linking unitselected from the group consisting of direct bond, alkylidene, secondaryor tertiary amine, oxygen, sulfide, sulfone, and sulfoxide.

[0055] The phosphorus-containing bidentate ligand (monomer) compoundsrepresented by Formulas I and II comprise bidentate phosphites(compounds of Formula I or II having three phosphorus to oxygen bonds),phosphinites (compounds of Formula I or II having one phosphorus tooxygen bond and two phosphorus to carbon bonds), phosphonites (compoundsof Formula I or II having two phosphorus to oxygen bonds and onephosphorus to carbon bond), and mixed phosphite/phosphinites,phosphite/phosphonites, phosphinite/phosphonites.

[0056] The bidentate phosphites (those compounds of Formula I or IIhaving three phosphorus to oxygen bonds) of the present invention can beprepared as described in European Pat. App. 92109599.8 of MitsubishiKasei Corporation and the corresponding U.S. Pat. No. 5,235,113,incorporated herein by reference. The reaction of a phosphorochloriditewith a binaphthol represented by Formula III wherein R′ is H or M willlead to a bidentate phosphite represented by Formula I. Similarly, thereaction of a phosphorochloridite with a biphenol represented by FormulaIV wherein R′ is H or M will lead to a bidentate phosphite representedby Formula II. U.S. Pat. Nos. 6,031,120 and 6,069,267 (incorporatedherein by reference) describe selective synthesis of bidentate phosphitecompounds. For example, the phosphorochloridite can be prepared in-situfrom phosphorus trichloride and a phenol such as o-cresol and thentreated in the same reaction vessel with an aromatic diol to give thebidentate phosphite. When R′ is H, it is preferred to have astoichiometric excess of a base present during the phosphonylation todrive the reaction by salt formation with hydrogen chloride beinginherently co-produced. Preferably the base is a trialkylamine. Morepreferably, the trialkylamine is one with C₁ to C₁₂ branched or straightchain alkyl groups. Most preferred is triethylamine.

[0057] The bidentate phosphinite compounds of the present invention(those compounds of Formula I and Formula II having one phosphorus tooxygen bond and two phosphorus to carbon bonds) and bidentatephosphonite compounds (those compounds of Formula I and Formula IIhaving two phosphorus to oxygen bonds and one phosphorus to carbon bond)may be synthesized by phosphonylation of structures represented byFormulas III and IV with diarylchlorophosphine and ClP(Ar)(—O—Ar)respectively. See, for example, U.S. Pat. No. 5,523,453, incorporatedherein by reference, which describes preparation of bidentatephosphinites.

[0058] Alternatively, the phosphonylation reaction can be carried out bya process as described in U.S. Pat. No. 5,910,600. The first step is toconvert the phenolic groups of the substituted binaphthol and/orsubstituted biphenol to -OM groups, wherein M is an alkali metal or analkaline earth metal, followed by treatment with the phoshonylatingagent such as phosphorochloridite to give the organodiphosphitecompound.

[0059] The second aspect of the invention is a process for preparingcertain phosphorus-containing bidentate ligand (monomer) compoundscomprising those compounds of Formula I, wherein a is 1 or 2 and b is 0or 1 with the condition that a+b=2, or those compounds of Formula II,wherein a is 1 or 2 and b is 0 or 1 with the condition that a+b=2, saidprocess comprising:

[0060] (1) reacting at least one of acryloyl chloride or methacryloylchloride with a polyhydric alcohol to make at least one of monoacrylateor monomethacrylate,

[0061] (2) reacting at least one of the monoacrylate or monomethacrylatewith at least one of phosphorus trichloride or phosphorodichloridite oraryldichlorophosphine (Cl₂P—Ar) to give at least one ofphosphorochloridite- or aryl,aryloxychlorophosphinite-containingacrylate or methacrylate,

[0062] (3) reacting at least one of the phosphorochloridite- oraryl,aryloxychlorophosphinite-containing acrylate and/or methacrylatefrom step (2) with at least one compound of Formula III and/or at leastone compound of Formula IV, wherein each R′ individually is hydrogen orM, wherein M is an alkali metal or an alkaline earth metal.

[0063] The term “polyhydric alcohol” used herein refers to, unlessotherwise indicated, a molecule having two or more hydroxyl groups. Eachhydroxyl group is attached to an aromatic ring, Ar², wherein each Ar² isindependently selected from the group consisting of C₆ to C₄₀ phenylene,C₁₀ to C₄₀ naphthylene, and combinations thereof. Examples of polyhydricalcohols include, but are not limited to, those illustrated below:

[0064] The preferred polyhydric alcohol is a diol wherein each hydroxylis attached to an aromatic group selected from the group consisting ofphenylene and naphthylene and the aromatic group is further substitutedwith a primary alkyl or secondary alkyl or cycloalkyl group ortho to theoxygens.

[0065] The polyhydric alcohol is contacted with acryloyl chloride ormethacryloyl chloride to generate a solution containing acrylates ormethacrylates. Depending on the structure of the polyhydric alcohol,di-, tri-, and higher order acrylates and methacrylates can begenerated. An organic base such as trialkylamine is used to react withthe resultant HCl. The mixture can be purified by methods known in theart; for example, column chromatography can be used. The acrylate ormethacrylate has one or more reactive aromatic alcohol groups that canreact with phosphorodichloridite or phosphorus trichloride or aryldichlorophosphine or mixture thereof to form phosphorochloridite ordiaryl chlorophosphine or mixture thereof. The preferredphosphorodichloridite has the formula selected from the group consistingof Cl₂P(O—Ar—R), wherein the R group is preferably ortho to the oxygen.The most preferred phosphorodichloridites are those derived from phenolscontaining one ortho substituent that is primary or secondary alkyl orcycloalkyl of 1 to 12 carbon atoms.

[0066] The use of mixtures of ClP(Ar)(—O—Ar) and diarylchlorophosphinewith an aromatic diol will give a bidentate phosphorus compound withboth phosphonite and phosphinite groups. The use of mixtures ofphosphorochloridite and diarylchlorophosphine with an aromatic diol willgive a bidentate phosphorus compound with both phosphite and phosphinitegroups. The use of mixtures of phosphorochloridite and ClP(Ar)(—O—Ar)will give a bidentate phosphorus compound with both phosphite andphosphonite groups.

[0067] Typically the pair of trivalent phosphorus atoms is incorporatedinto the bidentate ligand moiety (i.e., into a compound of Formula I orFormula II) by reacting a diarylchlorophosphonite (ClP(Ar)₂),diaryloxychlorophosphonite (ClP(—O—Ar)₂), anaryl,aryloxychlorophosphinite (ClP(Ar)(—O—Ar)) or the like with thehydroxyl groups of a 2,2′-dihydroxyl-1,1′-binaphthalene or a2,2′-dihydroxyl-1,1′-biphenylene structure. As such, any protected diolstructure is converted (e.g., hydrolyzed, protonated, or the like) backto the hydroxyl group prior to phosphonylation. Preferably thephosphonylation reaction [producing what is referred to herein as adiaryloxyphonite unit (—P(—O—Ar)₂), a diarylphosphine unit (—P(Ar)₂), oraryl,aryloxyphosphinite unit (—P(Ar)(—O—Ar)) or mixture thereof] isperformed with at least one stoichiometric equivalent of thediarylchlorophosphonite (ClP(Ar)₂), or diaryloxychlorophosphonite(ClP(—O—Ar)₂), or aryl,aryloxychlorophosphinite (ClP(Ar)(—O—Ar)) ormixture thereof for each hydroxyl in the diol structure. Advantageously,a stoichiometric excess of a trialkylamine or the like is present duringthe phosphonylation to drive the reaction by salt formation withhydrogen chloride being inherently co-produced. Again the aryl (Ar) isselected from the group consisting of phenyl, naphthyl, substitutedphenyl, and substituted naphthyl with the proviso that, for anyindividual phosphorus, the pair of aryls or aryloxys or combination ofaryl and aryloxy may optionally be linked to each other either directlyor through a linking unit. When the aryl is a substituted phenyl ornaphthyl, the substitution on the aromatic ring preferably involves aradical or radicals selected from the group consisting of C₁ to C₂₀branched or straight chain alkyl, C₁ to C₂₀ cycloalkyl, acetal, ketal,perhaloalkyl, cyclic ether, CN, —CHO, F, Cl, C₆ to C₂₀ aryl, —OR¹,—CO₂R¹, —S(O)R¹, —SO₂R¹, —SO₃R¹, and —C(O)R¹; where each R¹ isindependently selected from the group consisting of C₁ to C₂₀ branchedor linear alkyl, C₁ to C₂₀ cycloalkyl and C₆ to C₂₀ aryl. In a preferredembodiment, one of the substitutents ortho to the oxygen in the O—Argroup is hydrogen, and the other substituent ortho to the oxygen isselected from the group consisting of C₁ to C₂₀ branched or linearalkyl, C₁ to C₂₀ cycloalkyl, acetal, ketal, C₆ to C₂₀ aryl, cyclicether, and OR¹, where each R¹ is independently selected from the groupconsisting of C₁ to C₂₀ branched or linear alkyl, C₁ to C₂₀ cycloalkyland C₆ to C₂₀ aryl.

[0068] The two aryl groups associated with the phosphorus atom of adiaryloxyphosphonite unit (—P(—O—Ar)₂), or a diarylphosphine unit(—P(Ar)₂), or aryl, aryloxyphosphine unit (—P(Ar)(—O—Ar)) may be linkedto each other either directly through an aryl carbon to aryl carbon bondor through a linking unit, with the linking unit preferably selectedfrom the group consisting of —O—, —S—,—S(O)—, —S(O)₂—, —C(R²)(R²)—, andN(R²)—; where each R² is independently selected from the groupconsisting of H, C₁ to C₂₀ branched or linear alkyl, C₁ to C₂₀cycloalkyl, and C₆ to C₂₀ aryl.

[0069] Examples of diarylchlorophosphonite (ClP(Ar)₂),diaryloxychlorophosphonite (ClP(—O—Ar)₂), aryl,aryloxychlorophosphinite(ClP(Ar)(—O—Ar)) phosphorochloridites useful for phosphonylationinclude, but are not limited to, those shown below:

[0070] The phosphorochloridite for phosphonylation can be prepared byany means known to one skilled in the art. For example, thephosphorochloridite may be prepared by contacting one molar equivalentof PCl₃ with about two molar equivalents of substituted phenol at atemperature between about −40° C. to 10° C. in the absence of an organicbase. The resulting solution is then treated with at least twoequivalents of a base, such as an organic base, to produce aphosphorochloridite. When the substituted phenols are replaced withsubstituted biphenol or substituted alkylidenebisphenol, thephosphorochloridite is similarly prepared by mixing one molar equivalentof PCl₃ with about one molar equivalent of substituted biphenol orsubstituted alkylidenebisphenol at a temperature between about −40° C.and 10° C. in the absence of an organic base. The resulting solution isthen treated with at least two equivalents of an organic base to producea phosphorochloridite.

[0071] When preparing the phosphorochloridite in the above manner, it isimportant to maintain temperature in the range of −40° C. to 10° C.during the base addition. Since the addition of base results in theformation of an insoluble salt by neutralizing HCl, the reaction mixturecan become viscous, making it difficult to achieve good mixing of thebase. Good mixing is important to avoid temperature gradients in thereaction mixture which can decrease yield of the desired product. Thereaction should be conducted with vigorous stirring or other agitationto allow effective removal of heat from the reaction mixture. Cooling tothe required temperature range can be accomplished by techniques wellknown in the art. The base used in preparing the ligands is generallyanhydrous and soluble in the reaction medium. Suitable bases are organicamines. Especially preferred are trialkylamines. The most preferredbases are selected from the group consisting of tributylamine,benzyldimethylamine, triethylamine, diisopropylmethylamine, andcombinations of two or more thereof.

[0072] The phosphorochloridite can also be prepared by other methodsknown in the art. For example, one method involves treating phenols withPCl₃, such as described in Polymer, 1992, 33, 161; Inorg. Syn., 1996, 8,68; U.S. Pat. No. 5,210,260; PCT Pat. App. WO 9622968; and Z. Anorg.Allg. Chem., 1986, 535, 221; incorporated herein by reference. When thephosphorochloridite cannot be prepared in good yield from PCl₃, thepreferred method involves the treatment ofN,N-dialkyl,diarylphosphoramidite derivatives with HCl. TheN,N-dialkyl,diarylphosphoramidite is of the form (R³)₂NP(aryloxy)₂ whereR³ is a C₁ to C₄ alkyl group, and can be obtained by reacting phenol orsubstituted phenol with (R³)₂NPCl₂ by methods known in the art, such asdisclosed in WO 9622968, and U.S. Pat. Nos. 5,710,306 and 5,821,378,incorporated herein by reference. The N,N-dialkyl,diarylphosphoramiditescan be prepared, for example, as described in Tet. Lett., 1993, 34,6451; Synthesis, 1988, 2, 142; and Aust. J. Chem., 1991, 44, 233.

[0073] For example, the reaction of phosphorus trichloride with oneequivalent of substituted phenol will lead to Cl₂P—O—Ar, an aryloxyphosphorodichloridite. The Cl₂P—O—Ar can also be prepared from((alkyl)₂N)PCl₂ with a substituted phenol followed by treatment withHCl. The reaction of Cl₂P—O—Ar with a divalent bridging group such as asubstituted biphenol or substituted binaphthol in the presence of basewill lead to a monodentate phosphite. The reaction of Cl₂P—O—Ar withpolymers containing hydroxylated biaryls in the presence of base willlead to polymers containing monodentate phosphite moieties. Preferredbases are organic bases such as trialkylamines. The use of mixtures ofaryldichlorophosphine and diarylchlorophosphine [Cl₂P(—O—Ar),ClP(—O—Ar)₂, Cl₂P(Ar), ClP(Ar)₂] with polymers containing hydroxylatedbiaryls will give polymers containing bidentate phosphinite, bidentatephosphite, monodentate phosphinite, and monodentate phosphite groups.Similarly, mixtures containing ClP(Ar)(—O—Ar), ClP(—O—Ar)₂, and ClP(Ar)₂will lead to polymers containing bidentate phosphonite, bidentatephosphite and bidentate phosphinite groups. Other combinations arepossible.

[0074] Phosphorochloridite can be prepared from the reaction ofphosphorodichloridite with a phenol. An example is the reaction ofo-cresol with the phosphorodichloridite of isopropylphenol to give thephosphorochloridite as depicted below.

[0075] The resultant phosphorochloridite is contacted with an aromaticdiol selected from at least one of Formulas III and IV wherein R′ is Hor M, wherein M is an alkali metal or alkaline earth metal, to prepare acomposition comprising at least one compound of Formula I and/or atleast one compound of Formula II. The case wherein R′ is M is describedin U.S. Pat. No. 5,910,600.

[0076] An example is shown below:

[0077] In the third aspect, the present invention provides a method formaking a polymeric, phosphorus-containing composition by heating, in thepresence of an initiator, preferably a free radical initiator (to effectpolymerization), a composition comprising at least one compound ofFormula I and/or at least one compound of Formula II, provided at leastone R represents ethenyl, propenyl, acryloyl, methacryloyl or theorganic radical with a terminal ethenyl, propenyl, acryloyl, ormethacryloyl group or at least one R″ represents ethenyl, propenyl, orthe organic radical with a terminal ethenyl or propenyl group.

[0078] Polymerization can be carried out using known methods forpolymerization of ethylenic monomers described in the prior art. Thepolymerization of ethylenic monomers may be initiated with a freeradical, carbanion, or carbonium ion. The preferred initiator is a freeradical initiator, such as 2,2′-azobisisobutyronitrile (AIBN) or2,2′-azobis(2-methylpropanenitrile). For example, a compositioncomprised of vinylic derivative of compounds of Formula I and/or FormulaII (1-100 mol %) and one or more different comonomers (e.g., styrene ordivinylbenzene) (1-99 mol %) are dissolved in an organic solvent (e.g.,toluene or tetrahydrofuran). A free radical initiator (e.g.,azobisisobutyronitrile, AIBN) is added. The mixture is held atatmospheric pressure and a temperature of 20° C. to 150° C. for 1 to 100hours to produce a polymeric composition.

[0079] The method of making compounds of Formulas I and/or II generallyresults in a mixed product containing not only the compounds of FormulasI and/or II, but also other products, including monodentate phosphoruscompounds. These compositions may be used as-prepared to produce thepolymeric composition. Alternatively, the compounds of Formula I and/orII may be isolated and treated in a purified form. If the composition ofFormula I and/or II is used as-prepared to make the polymer, the polymermay contain monodentate phosphites, etc. in addition to compounds ofFormula I and/or II.

[0080] Compositions comprising the compounds of Formulas I and/or II mayalso contain comonomers:

[0081] (1) not within the scope of the compounds of Formula I and/or II;

[0082] (2) selected from the monomers represented by Formulas III andIV; as well as

[0083] (3) other monomers containing vinyl and acrylate groups.

[0084] Some representative comonomers include, but are not limited to:methyl acrylate, bisphenol A dimethacrylate, the diacrylate of2,2-bis(4-hydroxy-3-methylphenyl)propane, the monoacrylate of2,2-bis(4-hydroxy-3-methylphenyl)propane, divinylbenzene,1,1,1-trimethylolpropane trimethacrylate, ethylene glycoldimethylacrylate, pentaerythritol tetraacrylate, hydroquinonediacrylate, benzyl acrylate, methyl methacrylate, styrene,4-tertbutylstyrene, alpha-methylstyrene, 2,5-dimethylstyrene, and2-vinylnaphthalene.

[0085] In the fifth aspect, the present invention also provides a methodto produce a polymeric ligand, which may or may not be identical to thatdescribed previously, wherein a composition comprising at least onecompound of Formula III and/or at least one compound of Formula IV isheated in the presence of an initiator, followed by phosphonylation ofthe resultant polymeric precursor to produce a polymeric compositioncomprising trivalent phosphorus atoms.

[0086] The polymeric precursor may be formed by contacting a compositioncomprising at least one compound of Formula III and/or at least onecompound of Formula IV, wherein each R′ individually is hydrogen, analkali metal, an alkaline earth metal or a hydroxyl-protective groupselected from alkyl, alkoxyalkyl (e.g., CH₃OCH₂—), carbonylalkyl (e.g.,CH₃—C(O)—), and a crown ether formed by linking both R′ groups together,with an initiator, preferably a free radical initiator, and heating theresulting mixture to a preselected temperature for a preselected timesufficient to permit reaction, and phosphonylating the resultingpolymer.

[0087] The term “phosphonylation” means that each hydrogen or protectinggroup of the hydroxyl groups or protected hydroxyl groups of therespective 2,2′-dihydroxyl-1,1′-binaphthalene or2,2′-dihydroxyl-1,1′-biphenylene structures is replaced with atrifunctional phosphorus. Typically (after removal of the protectivegroups by hydrolysis or the like), the hydroxyl groups are reacted witha diaryloxychlorophosphonite (ClP(—O—Ar)₂), a diarylchlorophosphine(ClP(Ar)₂), or an aryl,aryloxychlorophosphinite (ClP(Ar)(—O—Ar)), ormixtures thereof, producing a phosphorus-to-oxygen chemical bond withthe elimination of hydrogen chloride or an equivalent. Alternatively,the hydroxyl groups (—OH) can be converted to alkoxides (—OM) wherein Mis an alkali metal or alkaline earth metal. Treatment with adiaryloxychlorophosphonite (ClP(—O—Ar)₂), a diarylchlorophosphine(ClP(Ar)₂), or an aryl,aryloxychlorophosphinite (ClP(Ar)(—O—Ar)), ormixtures thereof produces a phosphorus-to-oxygen chemical bond with theelimination of metal chloride (metal being M) or an equivalent.

[0088] Compounds of Formulas III and IV containing ethylenic groups(containing a double bond) can be prepared by reaction of thecorresponding halide derivative with ethylene under typicalHeck-coupling conditions. Typical reaction conditions for Heck-couplingare described in Organic Reactions, 1982, 27, 348; Acc. Chem. Res.,1995, 28, 2; and Pure & Appl. Chem., 1978, 50, 691. For example,6,6′-dibromo-2,2′-dihydroxy-1,1′-binaphthyl is reacted with Pd(OAc)₂ (5mol %), P(o-tolyl)₃ (15 mol %) under pressure of ethylene (200 psi) at75° C., as is shown below.

[0089] Examples of compounds of Formulas III and IV useful as startingmonomer include, but are not limited to, those shown below:

[0090] Preferred compounds are those of Formula III, wherein a=2, b=0, Ris primary or secondary alkyl located ortho to the oxygen bonded to Ar,wherein y≧1, and wherein at least one R″ is primary or secondary alkylgroup and is located at the ortho position of the oxygen bonded to thebinaphthalene group, or a compound of Formula IV wherein a=2, b=0, R isprimary or secondary alkyl located ortho to the oxygen bonded to Ar,wherein x≧1 and wherein at least one R″ is primary or secondary alkylgroup and is located at the ortho positions of the oxygen bonded to thebiphenylene group.

[0091] Similar to aspect three, the polymerization of a compositioncomprising at least one monomer of Formula III and/or at least onemonomer of Formula IV can be carried out using known methods forpolymerization of ethylenic monomers described in the prior art. Thepolymerization of ethylenic monomers can be initiated with a freeradical, carbanion, or carbonium ion. The preferred initiator is a freeradical initiator, specifically 2,2′-azobisisobutyronitrile (AIBN) or2,2′-azobis(2-methylpropanenitrile). For example, the mixture could beheated in the presence of a free radical initiator at atmosphericpressure and a temperature of 20° C. to 150° C. for 1 to 100 hours toproduce a polymeric composition.

[0092] The polymerization may be carried out in the presence ofcomonomers, which can be selected from the monomers represented byFormulas I and II, as well as other monomers containing vinyl andacrylate groups. Some representative comonomers include, but are notlimited to: methyl acrylate, bisphenol A dimethacrylate, the diacrylateof 2,2-bis(4-hydroxy-3-methylphenyl)propane, the monoacrylate of2,2-bis(4-hydroxy- 3-methylphenyl)propane, divinylbenzene, styrene,1,1,1-trimethylolpropane trimethacrylate, ethylene glycoldimethylacrylate, pentaerythritol tetraacrylate, hydroquinonediacrylate, benzyl acrylate, and methyl methacrylate.

[0093] As used herein, the structures used in Formulas I, II, III, andIV, and the expressions “2,2′-dihydroxyl-1,1′-binaphthalene” and“2,2′-dihydroxyl-1,1′-biphenylene” denote not only the diol structure,but also the corresponding so-called protected diol structures whereinthe hydrogen of the hydroxyl group is temporarily replaced by variousorganic radicals as generally known in the art. Therefore, thepolymerization and/or copolymerization of the vinyl- oracrylate-substituted 2,2′-dihydroxyl-1,1′-binaphthalene or2,2′-dihydroxyl-1,1′-biphenylene (or mixtures thereof), can, inprinciple, be performed either in the diol or the protected diol form.In the protected form of Formulas III and IV, protecting groups areprovided on any naphtholic or phenolic hydroxyl groups prior topolymerization and then preferably removed prior to phosphonylation.Suitable protecting groups include ethers, alkyls, esters, and crownethers. Other protecting groups as generally known to those skilled inthe art of protecting hydroxyl moieties during reactions are suitablefor this purpose.

[0094] In its seventh aspect, the present invention further provides amethod to produce a polymeric, phosphorus-containing composition byheating a phosphorochloridite containing at least one acrylate or methylacrylate group in the presence of an initiator, preferably a freeradical initiator, to produce a polymer containing phosphorochloridite,and further reacting this polymer with a composition comprising at leastone compound of Formula III and/or Formula IV wherein each R′individually is H or M, with the provision that if R′ is protected, theprotecting group must be removed before reacting the compound of FormulaIII and/or Formula IV with the polymer containing phosphorochloridite.

[0095] Preferred compounds are when the trivalent phosphorus is adiaryloxyphosphite unit, —P(—O—Ar)₂, and a compound of Formula III,wherein a=2, b=0, the Ar group contains a primary or secondary alkyllocated ortho to the oxygen bonded to Ar, wherein y≧1 and wherein atleast one R″ is primary or secondary alkyl group and is located at theortho position of the oxygen bonded to the binaphthalene group, or acompound of Formula IV wherein a=2, b=0, the Ar group contains a primaryor secondary alkyl located ortho to the oxygen bonded to Ar, wherein x 1and wherein at least one R″ is primary or secondary alkyl group and islocated at the ortho positions of the oxygen bonded to the biphenylenegroup.

[0096] The phosphorochloridite for use in the seventh aspect may beprepared as described above. Heating the phosphorochloridite in thepresence of an initiator provides a polymeric phosphorochloridite.Contacting the polymeric phosphorochloridite with the compositioncomprising at least one compound of Formula III and/or Formula IVprovides the polymeric, phosphorus-containing composition.

[0097] The above processes describe the synthesis of polymeric,phosphorus-containing ligands of various structures. It is known in theart that the solubility properties of polymers are affected by theirstructure. It is preferred that the polymeric ligands of this inventionbe as insoluble as possible, consistent with retaining substantialcatalytic activity. If the resulting polymers are insoluble, they can beseparated by filtration from the reaction mixtures in which they areused and then recycled. If the polymeric ligands are partially solublein the reaction mixture, they can be separated by filtration of theinsoluble ligand and then precipitation of the soluble ligand with asolvent in which the ligand has extremely low solubility or byprecipitation of the soluble ligand and filtration of the reactionmixture. If the ligands are completely soluble in the reaction mixture,they can be separated by precipitation with a solvent in which theligand has extremely low solubility.

Use of the Present Phosphorus-Containing Ligands in CatalystCompositions

[0098] In the ninth aspect, the present invention provides a catalystcomposition, optionally containing a Lewis Acid, comprising at least onemonomeric ligand composition of Formulas I and/or II combined with atleast one Group VIII transition metal, transition metal compound, and/ortransition metal complex, or at least one polymeric ligand compositionof the present invention combined with at least one Group VIIItransition metal, transition metal compound, or transition metalcomplex, and/or the catalyst material of aspect three of the presentinvention wherein the polymerization is carried out in the presence ofat least one Group VIII transition metal, transition metal compound, ortransition metal complex. Generally, any Group VIII metal or metalcompound can be used to combine with the composition. The term “GroupVIII” refers to the ACS version of the Periodic Table of the Elements,“CRC Handbook of Chemistry and Physics”, 67^(th) edition, Boca Raton,Fla.: CRC Press, 1986-1987.

[0099] Generally, a Group VIII metal or compound thereof is combinedwith at least one monomeric or polymeric ligand of the present inventionto provide the catalyst. Among the Group VIII metal compounds, nickel,cobalt, and palladium compounds are preferred for hydrocyanationcatalysts. A nickel compound is most preferred. A zero-valent nickelcompound that contains a ligand that can be displaced by the polymericligand of the present invention is the most preferred source of GroupVIII metal or Group VIII metal compound. Zero-valent nickel compoundscan be prepared or generated according to methods known in the art, suchas those described in U.S. Pat. Nos. 3,496,217; 3,631,191; 3,846,461;3,847,959; and 3,903,120; incorporated herein by reference. Threepreferred zero-valent nickel compounds are Ni(COD)₂ (COD is1,5-cyclooctadiene), Ni{P(O-o-C₆H₄CH₃)₃}₃ andNi{P(O-o-C₆H₄CH₃)₃}₂(C₂H₄), as known in the art.

[0100] Alternatively, divalent nickel compounds can be combined with areducing agent to serve as a source of zero-valent nickel in thereaction. Suitable divalent nickel compounds include compounds of theformula NiZ² ₂ where Z² is halide, carboxylate, or acetylacetonate.Suitable reducing agents include metal borohydrides, metal aluminumhydrides, metal alkyls, Li, Na, K, or H₂. Elemental nickel, preferablynickel powder, when combined with a halogenated catalyst, as describedin U.S. Pat. No. 3,903,120 (incorporated herein by reference) is also asuitable source of zero-valent nickel.

[0101] The chelating arrangement of donor atoms in bidentate ligandsresults in a strong ligand-metal interaction and thus greatly minimizesthe potential for metal leaching. It is possible to alter the spacingbetween the chelating atoms, the steric environment of these atoms, andthe electronic properties of the donor atoms, offering control of ligandcoordination properties, thereby optimizing catalyst performance.

Hydrocyanation Using the Present Phosphorus-Containing Ligands

[0102] In the tenth aspect of the present invention, the monomers ofFormulas I and/or II and/or the polymeric ligand compositions of thepresent invention may be used to form catalysts (with or without a LewisAcid) which may be used for the hydrocyanation of organic compounds. Theprocess comprises contacting, in the presence of the catalyst, anunsaturated organic compound with a hydrogen cyanide-containing fluidunder conditions sufficient to produce a nitrile, wherein the catalystcomprises a Group VIII metal, at least one of the present ligandsdescribed above, and optionally a Lewis acid. The term “fluid” may referto a gas, liquid, or mixture thereof. Any fluid containing about 1 to100% HCN can be used. Pure hydrogen cyanide may be used. Preferably, theHCN contains less than 40 ppm sulfuric acid, less than 20 ppm sulfurdioxide, less than 20 ppm cyanogen, less than 10 ppm epoxide, less than10 ppm carbon monoxide, less than 20 ppm acrylonitrile, and less than100 ppm peroxides.

[0103] The hydrocyanation process can be carried out, for example, bycharging a suitable vessel such as a reactor with an unsaturatedcompound, catalyst composition, and solvent, if any, to form a reactionmixture. Hydrogen cyanide can be initially combined with othercomponents to form the mixture. However, it is preferred that HCN beadded slowly to the mixture after the other components have beencombined. Hydrogen cyanide can be delivered as a liquid or as a vapor tothe reaction. As an alternative, a cyanohydrin can be used as the sourceof HCN, as described in, for example, U.S. Pat. No. 3,655,723,incorporated herein by reference. Preferably, the unsaturated compoundcontains less than 100 ppm peroxides.

[0104] Another suitable technique is to charge the vessel with thecatalyst and the solvent (if any) to be used, and feed both theunsaturated compound and the HCN slowly to the reaction mixture.

[0105] The molar ratio of unsaturated compound to catalyst can be variedfrom about 10:1 to about 100,000:1. The molar ratio of HCN to catalystgenerally is varied from about 10:1 to 100,000:1, preferably 100:1 to2,500:1, for a batch operation. In a continuous operation, such as whenusing a fixed bed catalyst type of operation, a higher proportion ofcatalyst can be used, such as 5:1 to 100,000:1, preferably 100:1 to5,000:1, HCN to catalyst.

[0106] Preferably the reaction mixture is agitated, for example bystirring or shaking. The reaction product can be recovered byconventional techniques such as distillation. The reaction can be runeither batchwise or continuously.

[0107] The hydrocyanation can be carried out with or without a solvent.The solvent, if used, can be liquid at the reaction temperature andpressure and inert towards the unsaturated compound and the catalyst.Suitable solvents include hydrocarbons such as benzene, xylene, orcombinations thereof; ethers, such as tetrahydrofuran (THF); nitriles,such as acetonitrile, benzonitrile, adiponitrile, or combinations of twoor more thereof. The unsaturated compound to be hydrocyanated can itselfserve as the solvent. Hydrocyanation can also be carried out in the gasphase.

[0108] The exact temperature is dependent to a certain extent on theparticular catalyst being used, the particular unsaturated compoundbeing used and the desired reaction rate. Normally, temperatures of from−25° C. to 200° C. can be used, the range of 0° C. to 150° C. beingpreferred.

[0109] Atmospheric pressure is satisfactory for carrying out thereaction, and hence pressures of from about 0.05 to 10 atmospheres (50.6to 1013 kPa) are preferred. Higher pressures, up to 10,000 kPa or more,can be used, if desired, but any benefit that may be obtained therebywould need to justify the increased cost of such operations.

[0110] The time required can be in the range of a few seconds to manyhours (such as 2 seconds to 24 hours), depending on the particularconditions and method of operation.

[0111] The unsaturated compound can have 2 to about 30 carbon atoms permolecule. It can have the formula of R⁴CH═CH—CH═CR⁵, CH═CH—(CH₂)_(q)—R⁶,CH₃—(CH₂)n—CH═CH—(CH₂)_(q)—R⁶, and combinations of two or more thereofin which R⁴ and R⁵ are each independently H, C₁ to C₃ alkyl, orcombinations thereof; R⁶ is H, CN, CO₂R⁷, perfluoroalkyl having 1 toabout 20 carbon atoms; n is an integer of 0 to 12; q is an integer of 0to 12 when R⁶ is H, CO₂R⁷ or perfluoroalkyl; q is an integer of 1 to 12wherein R⁶ is CN; and R⁷ is C₁ to C₁₂ alkyl or cycloalkyl, C₆ to C₂₀aryl, or combinations thereof.

[0112] The unsaturated compound can be an acyclic, aliphatic,monoethylenically unsaturated compound or cyclic unsaturated compound,or combinations thereof. Non-limiting examples of ethylenicallyunsaturated compounds are shown in Formulas V and VII, and thecorresponding terminal nitrile compounds produced are illustrated byFormulas VI and VIII, respectively, wherein R⁶ is the same as disclosedabove.

[0113] The hydrocyanation reaction yields internal as well as terminalnitriles. Preferred products are terminal nitriles. Starting compoundsof Formula V yield terminal nitriles of Formula VI, while those ofFormula VII yield terminal nitriles of Formula VIII.

[0114] Suitable unsaturated compounds include, but are not limited to,ethylenically unsaturated organic compounds containing from 2 to about30 carbon atoms. Examples of suitable ethylenically unsaturatedcompounds are ethylene, cyclohexene, propylene, 1-butene, 2-pentene,2-hexene, and combinations of two or more thereof. The unsaturatedcompound may also be diethylenically unsaturated such as allene. Othersuitable substituted, ethylenically unsaturated compounds are3-pentenenitrile, 4-pentenenitrile, methyl 3-pentenoate, combinations oftwo or more thereof, and ethylenically unsaturated compounds havingperfluoroalkyl substituents such as, for example, C_(b)F_(2b+1), where bis an integer of up to 20. The monoethylenically unsaturated compoundscan also be conjugated to an ester group such as methyl 2-pentenoate.Preferred unsaturated compounds are linear alkenes, linearalkenenitriles, linear alkenoates, linear alkyl 2-alkenoates,perfluoroalkyl ethylenes, and combinations of two or more thereof. Mostpreferred substrates include 3- and 4-pentenenitrile, alkyl 2-, 3-, and4-pentenoates, and C_(b)F_(2b+1)CH═CH₂ (where b is 1 to 12), andcombinations of two or more thereof. 3-Pentenenitrile and4-pentenenitrile are especially preferred olefins. Preferably, thepentenenitriles contain less than 100 ppm peroxides.

[0115] When non-conjugated, acyclic, aliphatic, monoethylenicallyunsaturated compounds are used, up to about 10% by weight of themonoethylenically unsaturated compound can be present in the form of aconjugated isomer, which itself may undergo hydrocyanation. For example,when 3-pentenenitrile is used, as much as 10% by weight thereof may be2-pentenenitrile (as used herein, the term “pentenenitrile” is intendedto be identical with “cyanobutene”). Suitable unsaturated compoundsinclude unsubstituted hydrocarbons, as well as hydrocarbons substitutedwith groups that do not attack the catalyst, such as the cyano group.

[0116] The preferred products are terminal alkane nitriles, lineardicyanoalkylenes, linear aliphatic cyanoesters,3-(perfluoroalkyl)propionitrile, and combinations of two or morethereof. Most preferred products are adiponitrile, alkyl5-cyanovalerate, C_(b)F_(2b+1)CH₂CH₂CN, where b is 1 to 12, andcombinations of two or more thereof.

[0117] The process of this invention can be carried out in the presenceof one or more Lewis acid promoters that affect both the activity andthe selectivity of the catalyst system. The promoter may be an inorganicor organometallic compound in which the cation is selected fromscandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper,zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium,rhenium, lanthanum, europium, ytterbium, tantalum, samarium, and tin.Examples include ZnBr₂, Znl₂, ZnCl₂, ZnSO₄, CuCl₂, CuCl, Cu(O₃SCF₃)₂,CoCl₂, Col₂, Fel₂, FeCl₃, FeCl₂, FeCl₂(THF)₂, TiCl₄(THF)₂, TiCl₂,ClTi(OiPr)₂, MnCl₂, ScCl₃, AlCl₃, (C₈H₁₇)AlCl₂, (C₈H₁₇)₂AlCl,(iso-C₄H₉)₂AlCl, Ph₂AlCl, PhAlCl₂, ReCl₅, ZrCl₄, NbCl₅, VCl₃, CrCl₂,MoCl₅, YCl₃, CdCl₂, LaCl₃, Er(O₃SCF₃)₃, Yb(O₂CCF₃)₃, SmCl₃, B(C₆H₅)₃,(C₆H₅)₃SnX, where X═CF₃SO₃, CH₃C₆H₅SO₃, or (C₆H₅)₃BCN and TaCl₅.Suitable promoters are further described in U.S. Pat. Nos. 3,496,217;3,496,218; and 4,774,353; the disclosures of which are incorporatedherein by reference. These include metal salts (such as ZnCl₂, Col₂, andSnCl₂), and organometallic compounds (such as R⁸AlCl₂, R⁸SnO₃SCF₃, andR⁸B, where R⁸ is an alkyl or aryl group). U.S. Pat. No. 4,874,884(incorporated herein by reference) describes how synergisticcombinations of promoters can be chosen to increase the catalyticactivity of the catalyst system. Preferred promoters include CdCl₂,FeCl₂, ZnCl₂, B(C₆H₅)₃, and (C₆H₅)₃Sn(CF₃SO₃), CH₃C₆H₅SO₃, or(C₆H₅)₃BCN. The mole ratio of promoter to Group VIII transition metalpresent in the reaction can be within the range of about 1:16 to about50:1.

[0118] Hydrocyanation can also be carried out with a conjugated olefin.With conjugated olefins, a Lewis acid promoter is optional. Examples ofconjugated olefins containing from about 4 to about 15, preferably 4 to10 carbon atoms are 1,3-butadiene, cis and trans-2,4-hexadienes, cis andtrans-1,3-pentadienes, and combinations of two or more thereof.Butadiene is especially preferred by reason of its commercial importancein the production of adiponitrile. Preferably, the butadiene containsless than 20 ppm t-butyl catechol, less than 500 ppm vinylcyclohexene,and less than 100 ppm peroxides.

[0119] The following Formulas IX and X illustrate some suitable startingconjugated olefins, wherein each one of R⁹ and R¹⁰, independently, is Hor a C₁ to C₃ alkyl group.

[0120] Formulas XI, XII, and XIII represent the products obtained from1,3-butadiene and HCN wherein 3PN denotes 3-pentenenitrile, 4PN is4-pentenenitrile, and 2M3BN is 2-methyl-3-butenenitrile.

[0121] The reaction of a conjugated olefin and a HCN-containing fluidcan be carried out in the same manner as that described above inrelation to monoethylenically unsaturated compounds.

Isomerization Using the Present Phosphorus-Containing Ligands

[0122] In the eleventh aspect of the present invention, the monomers ofFormulas I and/or II and/or the ligand compositions of the presentinvention may be used to form catalysts, which may be used for theisomerization of branched nitriles to linear nitriles. The isomerizationcomprises contacting an alkenyl nitrile with a catalyst disclosed above,under conditions sufficient to isomerize the alkenyl nitrile. Theprocess can be run with or without a Lewis acid. Examples of suitablealkenyl nitriles include, but are not limited to,2-alkyl-3-monoalkenenitriles, 3-alkenenitriles, or combinations thereof.The isomerization can be carried out under substantially similarconditions as described above in relation to hydrocyanation. Preferably,the branched nitrile contains less than 100 ppm peroxides.

[0123] The 2-alkyl-3-monoalkenenitrile used as the starting material inthe isomerization can be made by the hydrocyanation of a diolefin asdescribed above, or can come from any other available sources. Theolefinic double bond in the 2-alkyl-3-monoalkenenitriles used asstarting materials in the isomerization cannot be conjugated to thetriple bond of the cyano group. Suitable starting2-alkyl-3-monoalkenenitriles can also carry groups that do not attackthe catalyst, for example, another cyano group. Preferably, the starting2-alkyl-3-monoalkenenitriles contain from 5 to 8 carbon atoms, excludingany additional substitution. 2-Methyl-3-butenenitrile is an especiallyimportant starting material, because it is used to produce adiponitrile.Other representative nitrile starting materials include2-ethyl-3-butenenitrile and 2-propyl-3-butenenitrile.

[0124] When the starting nitrile is 2-methyl-3-butenenitrile (2M3BN,Formula XIII above), the isomerization products are 3PN and 4PN, asshown in Formulas XI and XII, above.

[0125] The isomerization process of this invention can be carried out,for example, at atmospheric pressure and at any temperature in the rangeof 10-200° C., preferably in the range of 60-150° C. The pressure is notcritical, however, and can be above or below atmospheric pressure, ifdesired. Any of the conventional batch or continuous flow procedures maybe used either in the liquid phase or in the vapor phase (with respectto the relatively volatile 2-methyl-3-butenenitrile reactant and linearpentenenitrile products). The reactor may be of any mechanically andchemically resistant material, and is usually of glass or an inert metalor alloy, such as nickel, copper, silver, gold, platinum, stainlesssteel, Monel® metal alloy or Hastelloy® metal alloy.

[0126] The process can be carried out in the absence or in the presenceof a solvent or diluent. Any solvent or diluent that is inert to, ornondestructive of, the catalyst can be used. Suitable solvents include,but are not limited to, aliphatic or aromatic hydrocarbons (hexane,cyclohexane, benzene), ethers (diethyl ether, tetrahydrofuran, dioxane,glycol dimethyl ether, anisole), esters (ethyl acetate, methylbenzoate), nitriles (acetonitrile, benzonitrile), or combinations of twoor more thereof.

[0127] The catalyst (complex of Group VIII metal, preferably nickel, andligand) is essentially nonvolatile, whereas the 2-methyl-3-butenenitrilereactant and the linear pentenenitrile products are relatively volatile.

[0128] Accordingly, in a continuous flow procedure, the catalyst can bea component of the flowing system in a slurry-liquid-phase operation. Itcan also be in a mobile non-flowing liquid state in a semi-vapor phaseoperation, or it may be in a fixed-bed state in a conventional flowingvapor-phase operation or flowing liquid-phase operation.

[0129] The time required for the isomerization process to obtain apractical level of conversion of, for example,2-alkyl-3-monoalkenenitrile, to linear alkenenitrile is dependent uponthe temperature of reaction, i.e., operation at lower temperaturegenerally requires a longer time than operation at a higher temperature.A practical reaction time can be in the range of a few seconds to manyhours (2 seconds to about 24 hours), depending on the particularconditions and method of operation.

[0130] The molar ratio of 2-alkyl-3-monoalkenenitrile to catalyst isgenerally greater than 1:1, usually in the range from about 5:1 to20,000:1, preferably 100:1 to 5,000:1, for a batch or continuousoperation.

Hydroformylation Using the Present Phosphorus-Containing Ligands

[0131] In the twelfth aspect of the present invention, the monomers ofFormulas I and/or II and/or the ligands of the present invention may beused to form catalysts that may be used for hydroformylation ofunsaturated organic compounds with 2 to 20 carbon atoms or cyclicunsaturated compound to produce corresponding aldehydes. The catalystcomprises a Group VIII metal or Group VIII metal compound combined withat least one ligand of the present invention. Preferred Group VIIImetals for hydroformylation reactions are rhodium, iridium, andplatinum, the most preferred being rhodium. The Group VIII metal may bein the form of a compound, such as a hydride, halide, organic acid salt,ketonate, inorganic acid salt, oxide, carbonyl compound, amine compound,or combinations of two or more thereof. Preferred Group VIII metalcompounds are Ir₄(CO)₁₂, IrSO₄, RhCl₃, Rh(NO₃)₃, Rh(OAc)₃, Rh₂O₃,Rh(acac)(CO)₂, [Rh(OAc)(COD)]₂, Rh₄(CO)₁₂, Rh₆(CO)₁₆, RhH(CO)(Ph₃P)₃,[Rh(OAc)(CO)₂]₂, [RhCl(COD)]₂, and combinations of two or more thereof(“acac” is an acetylacetonate group; “OAc” is an acetyl group; “COD” is1,5-cyclooctadiene; and “Ph” is a phenyl group). However, it should benoted that the Group VIII metal compounds are not necessarily limited tothe above listed compounds. Rhodium compounds suitable forhydroformylation can be prepared or generated according to techniqueswell known in the art, as described, for example, in PCT Pat. App.WO9530680; U.S. Pat. No. 3,907,847; and J. Am. Chem. Soc., 1993, 115,2066, incorporated herein by reference. Rhodium compounds that containligands which can be displaced by the present phosphite ligands are apreferred source of rhodium. Examples of such preferred rhodiumcompounds are Rh(CO)₂ (acac), Rh(CO)₂(C₄H₉COCHCO-t-C₄H₉), Rh₂O₃,Rh₄(CO)₁₂, Rh₆(CO)₁₆, Rh(O₂CCH₃)₂, Rh(2-ethylhexanoate), andcombinations of two or more thereof.

[0132] The amount of transition metal in the catalyst may be varied andmay be determined by balancing catalyst activity and process economy. Ingeneral, the molar ratio of ligand to transition metal generally can befrom about 1:1 to about 100:1, preferably from about 2:1 to about 20:1moles phosphorus per mole metal.

[0133] The reactant of the hydroformylation process is an unsaturatedorganic compound having at least one “C═C” bond in the molecule andpreferably 2 to about 20 carbon atoms. Examples of suitableethylenically unsaturated organic compounds include, but are not limitedto, linear terminal olefinic hydrocarbons (i.e., ethylene, propylene,1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene,1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and 1-dodecene);cyclic olefinic hydrocarbons (i.e., cyclohexene, cyclopentene); branchedterminal olefinic hydrocarbons (i.e., isobutene and 2-methyl-1-butene);linear internal olefinic hydrocarbons (i.e., cis- and trans-2-butene,cis- and trans-2-hexene, cis- and trans-2-octene, and cis- andtrans-3-octene); branched internal olefinic hydrocarbons (i.e.,2,3-dimethyl-2-butene, 2-methyl-2-butene and 2-methyl-2-pentene);terminal olefinic hydrocarbons; internal olefinic hydrocarbon mixtures(i.e., octenes, prepared by dimerization of butenes); cyclic olefins(i.e., cyclohexene, and cyclooctene); and combinations of two or morethereof.

[0134] Examples of suitable unsaturated compounds also include thosesubstituted with an unsaturated hydrocarbon group, including olefiniccompounds containing an aromatic substituent such as styrene,alpha-methylstyrene and allylbenzene.

[0135] The unsaturated organic compound can also be substituted with oneor more functional groups containing a heteroatom, such as oxygen,sulfur, nitrogen or phosphorus. Examples of theseheteroatom-substituted, ethylenically unsaturated, organic compoundsinclude vinyl methyl ether, methyl oleate, oleyl alcohol,3-pentenenitrile, 4-pentenenitrile, 3-pentenoic acid, 4-pentenoic acid,methyl 3-pentenoate, 7-octen-1-al, acrylonitrile, acrylic acid esters,methyl acrylate, methacrylic acid esters, methyl methacrylate, acrolein,allyl alcohol, 3-pentenal, 4-pentenal, and combinations of two or morethereof.

[0136] The hydroformylation process of the invention can be illustratedas follows:

[0137] In the above equations, R¹¹ is H, —CN, —CO₂R¹², —C(O)NR¹²R¹²,—CHO, —OR¹², OH, or combinations of two or more thereof; p is an integerfrom 0 to 12; and r is an integer from 0 to 12. Each R¹² isindependently selected from the group consisting of H, C₁ to C₂₀branched or straight chain alkyl, C₁ to C₂₀ cycloalkyl, and C₆ to C₂₀aryl.

[0138] Particularly preferred unsaturated organic compounds are3-pentenenitrile, 3-pentenoic acid, 3-pentenal, allyl alcohol, and alkyl3-pentenoate, such as methyl 3-pentenoate, and combinations of two ormore thereof, preferably the 3-pentenenitrile, 3-pentenoic acid,3-pentenal, allyl alcohol, and alkyl 3-pentenoate, such as methyl3-pentenoate, and combinations of two or more thereof. Impurities thatare detrimental to the catalyst should be kept to a minimum. Preferably,the unsaturated organic compounds contain less than 100 ppm peroxides.The linear aldehyde compound prepared by the present process startingwith one of these compounds can be used advantageously in thepreparation of ε-caprolactam, hexamethylenediamine, 6-aminocaproic acid,6-aminocapronitrile or adipic acid, which are precursors for nylon-6and/or nylon-6,6.

[0139] The hydroformylation process of the invention also can be carriedout with a mixture that comprises two or more unsaturated organiccompounds. For example, 3-pentenenitrile can be present in a mixturecontaining 4-pentenenitrile. Because the 4-isomer reacts in a similarfashion as the corresponding 3-isomer to the desired linear aldehyde, amixture of isomers can be used directly in the present process.

[0140] The 3-pentenenitrile may be present in mixtures containingimpurities that do not interfere with the hydroformylation reaction. Anexample of such an impurity is 2-pentenenitrile.

[0141] The hydroformylation process of the invention can be carried outby any means known to one skilled in the art, such as, for example, theone disclosed in U.S. Pat. No. 4,769,498, the disclosure of which isincorporated herein by reference. Generally, the process can be carriedout under any condition sufficient to effect the production of a desiredaldehyde. For example, the temperature can be from about 0° C. to 200°C., preferably from about 50 to 150° C., and more preferably from 85° to110° C. The pressure may vary from atmospheric pressure to 5 MPa,preferably from 0.1 to 2 MPa. The pressure is, as a rule, equal to thecombined hydrogen and carbon monoxide partial pressures. Inert gasesalso may be present; the pressure may vary from atmospheric pressure to15 MPa when inert gases are present. The molar ratio of hydrogen tocarbon monoxide is generally between 10:1 and 1:10, and preferablybetween 6:1 and 1:2 moles hydrogen/mole carbon monoxide. It is mostpreferred that a 1:1 ratio of carbon monoxide and hydrogen is used.

[0142] The amount of catalyst is selected so that favorable results canbe obtained with respect to catalyst activity and process economy. Ingeneral, the amount of transition metal in the reaction medium, whichcomprises an unsaturated organic compound, a catalyst composition, andsolvent (if present), can be between 10 and 10,000 ppm and morepreferably between 50 and 1,000 ppm, calculated as free metal.

[0143] The solvent may be the mixture of reactants of thehydroformylation reaction itself, such as the starting unsaturatedcompound, the aldehyde product and/or by-products. Other suitablesolvents include saturated hydrocarbons (i.e., kerosene, mineral oil, orcyclohexane), ethers (i.e., diphenyl ether or tetrahydrofuran), ketones(i.e., acetone, cyclohexanone), nitriles (i.e., acetonitrile,adiponitrile or benzonitrile), aromatics (i.e., toluene, benzene, orxylene), esters (i.e., methyl valerate, caprolactone),dimethylformamide, or combinations of two or more thereof.

[0144] The hydroformylation process can be run in solution or in the gasphase. When the hydroformylation is carried out in the vapor phase, thepreferred temperature range is from about 50° C. to about 180° C., mostpreferably from about 90° C. to 110° C. The temperature must be chosenhigh enough so as to maintain all of the reactants and products in thevapor phase, but low enough to prevent deterioration of the catalyst.The particular preferred temperature depends to some extent on thecatalyst being used, the olefinic compound being used, and the desiredreaction rate. The operating pressure is not particularly critical andcan be from about 0.1 to 1.0 MPa. The pressure and temperaturecombination must be chosen so as to maintain reactants and products inthe vapor phase. A given catalyst is loaded into a reactor, such as atubular reactor, taking care to avoid exposure of oxygen-sensitivecatalysts to oxygen from the air. A gaseous mixture of the desiredolefinic compound, carbon monoxide and hydrogen, along with any desireddiluent, such as nitrogen, helium or argon, is then passed through thereactor while contacting the catalyst. The reaction products aregenerally liquid at room temperature and are conveniently recovered bycooling. The reactor effluent can be directly connected to a samplingvalve and can be analyzed by gas chromatography. Aldehydic products,such as linear and branched butyraldehydes obtained fromhydroformylation of propylene, can be quantitatively separated andanalyzed using a 30M DB-Wax® capillary GC column.

[0145] For the hydrocyanation, isomerization, and hydroformylationprocesses described herein, a non-oxidizing environment is desirable inorder to retard oxidative deactivation of the catalyst. Accordingly, aninert atmosphere, e.g., nitrogen, is preferably used, although air canbe used, if desired, at the expense of loss of a proportion of thecatalyst acitivity through oxidation. Impurities that are detrimental tothe catalyst should be kept to a minimum.

[0146] The following examples are presented to further illustratespecific features and embodiments of the present invention includingvarious methods of preparing the polymeric substrate on which thephosphorus-containing ligand is to be formed and methods of forming thephosphorus-containing ligand compositions. The following examples arenot intended to be limiting. Similarly the specific reactions andcompounds when identified structurally by chemical formula are intendedto be illustrative of the reaction pathway for the formation of thepresent phosphorus-containing bidentate ligand compositions. It shouldbe appreciated that other species and distribution of products will bepresent, as generally known in the art, and that any performance dataassociated with such compositions was derived using the mixtureas-produced, without isolation or separation of the specific compounds,unless otherwise indicated. All parts, proportions, and percentages areby weight, unless otherwise indicated.

[0147] In the examples, 3PN stands for 3-pentenenitrile, ADN stands foradiponitrile, COD stands for 1,5-cyclooctadiene, THF stands fortetrahydrofuran, Vazo® 64 free radical initiator represents2,2′-azobis(2-methylpropanenitirile) from E. I. Du Pont de Nemours &Co., Inc.; AIBN stands for 2,2′-azobisisobutyronitrile, DVB stands fordivinylbenzene and oTTP stands for tris(o-tolyl) phosphite.

[0148] In evaluating the performance of the respectivephosphorus-containing ligand compositions, the following generalprocedures were employed unless otherwise noted:

[0149] Preparation of Catalyst for Hydrocyanation Reactions

[0150] Method A A catalyst solution is prepared by adding 0.0039 gramsof Ni(COD)₂ (0.014 mmol) dissolved in 0.320 mL toluene to a specifiedquantity of the respective phosphorus-containing polymeric ligandcomposition being evaluated dissolved in 0.200 mL toluene.

[0151] Method B The specified weight of Ni containing solid in areaction vial fitted with a septum cap is used as prepared for butadienehydrocyanation and for 2-methyl-3-butenenitrile (2M3BN) isomerizationand contacted with 0.125 mL of THF for 30 minutes before use in3-pentenenitrile hydrocyanation.

[0152] General Procedure for Reactions

[0153] Hydrocyanation of butadiene: If the catalyst was made accordingto method A, 0.074 mL of the above catalyst solution nominallycontaining about 0.0020 mmol Ni is added to each of 2 reaction vialsfitted with septum caps. If the catalyst was made by method B the wholecatalyst sample as specified is used. The reaction vials are cooled to−20° C. and 120 μL of a solution of HCN in valeronitrile (0.830 mmolHCN) and 280 μL of a solution of butadiene (BD) in toluene (0.925 mmolBD) are added to each vial. The vials are sealed and placed in a hotblock reactor set at 80° C. Samples are removed after 3 hours andquenched by cooling to −20° C. The reaction mixtures are then diluted inethyl ether and the product distribution analyzed by GC againstvaleronitrile as an internal standard. The results are presented asrelative percent of the starting HCN that had been converted to usefulnitriles (3-pentenenitrile (3PN), and 2-methyl-3-butenenitrile (2M3BN)).

[0154] Isomerization of 2-methyl-3-butene nitrile (2M3BN): If thecatalyst was made according to method A, 0.082 mL of the above catalystsolution nominally containing about 0.0022 mmol Ni is added to each of 2reaction vials fitted with septum caps. If the catalyst was made bymethod B, the whole catalyst sample as specified is used. 130 μL of acold solution containing 2M3BN and valeronitrile (0.930 mmol 2M3BN) areadded to the reaction vials. The vials are sealed and placed in a hotblock reactor set at 125° C. Samples are removed after 3.0 hrs, cooledand diluted in ethyl ether. The product distribution is analyzed by GCusing valeronitrile as an internal standard. The results are presentedas the 3PN/2M3BN ratio.

[0155] Hydrocyanation of 3-pentenenitrile (3PN): If the catalyst wasmade according to method A, 0.116 mL of the above catalyst solutionnominally containing about 0.00312 mmol Ni is added to each of 2reaction vials fitted with septum caps. If the catalyst was made bymethod B, the whole catalyst sample as specified is used. 13 μL of asolution of ZnCl₂ in 3PN (0.0067 mmol ZnCl₂) is added to the catalystsample in a reaction vial with fitted with a septum cap. The vial iscooled to −20° C. and 125 μL of a solution of HCN, 3PN, and2-ethoxyethyl ether (0.396 mmol HCN, 0.99 mmol 3PN) are added. The 3PNused for hydrocyanation and hydroformylation contained approximately 97%t-3-pentenenitrile (GC). The vial is sealed and set aside for 24 hoursat room temperature. The reaction mixture is diluted with ethyl etherand the product distribution analyzed by GC using 2-ethoxyethyl ether asan internal standard. The results are presented as the relative percentof the starting pentenenitriles that have been converted to dinitrileproduct and the percent yield based on HCN. The selectivity to thelinear adiponitrile (ADN) isomer is reported as percent ADN in reactionproduct mixture.

[0156] Hydrocyanation of 3-pentenenitrile was also performed by slowlyadding the HCN to the reaction mixture. The catalyst composition and3-pentenenitrile were heated in a thermostatically controlled oil bath.HCN was delivered to the flask as an HCN/N₂ gas mixture by bubbling drynitrogen carrier gas through liquid HCN maintained in an ice bath at 0°C. This provided a vapor stream that was about 35% by volume HCN. Therate of nitrogen gas flow determined the rate of HCN delivery. Sampleswere periodically analyzed by gas chromatography (GC).

[0157] Hydroformylation of 3-pentenenitrile: Hydroformylationexperiments were performed according to the following procedure. In adrybox, a solution containing 3-pentenenitrile (5.0 g), Rh(CO)₂(acac)(2.5 mg), and 1,2-dichlorobenzene (internal standard, 0.27 M) wasprepared. This solution was added to a glass-lined pressure vesselcontaining approximately two molar equivalents of the supportedphosphorus compound per equivalent of rhodium. The reactor was sealed,pressurized to 65 psig with a 1:1 molar ratio of CO/H₂ and heated to 95°C. for 3 hours. The reactor was cooled and depressurized and a sample ofthe reaction mixture was analyzed by gas chromatography on an HP 5890AChromatograph with a DB5 fused silica capillary column (30 meters, 0.32mm I.D., 0.25 m film thickness) purchased from J. B. Scientific.

EXAMPLES Example 1

[0158] Aspect 2: Preparation of ethylenically unsaturated,phosphorus-containing bidentate ligand (1): Under nitrogen atmosphere, a100 mL flask with magnetic stir bar was charged with 2.450 grams of2,2-bis(4-hydroxy-3-methylphenyl)propane, 0.865 grams of acryloylchloride, 40 mL of toluene and 8 mL of THF. The mixture was cooled to−30° C. and 1.2 grams of triethylamine in 15 mL of toluene was added.About a quarter of the solvent was removed under vacuum and the mixturecooled to −30° C. To this mixture was added 2.266 grams of thephosphorodichlorodite of 2-isopropylphenol and 1.2 grams oftriethylamine in 10 mL of toluene. The mixture was stirred for one andone-half hours and cooled to −30° C. To the mixture was added 1.157grams of 3,3′,5,5′-tetramethyl-2,2′-biphenol and 1.2 grams oftriethylamine. The mixture was kept at −30° C. overnight and thenfiltered. Solvent was removed to give 5.978 grams of a tacky brown solid(³¹P NMR in CDCl₃: 142.21, 142.15, 135.20, 135.11, 134.74, 134.29,132.01, 131.96, and 131.13).

Example 1A

[0159] Aspect 9: Preparation of catalyst: 50 mg (0.042 mmol) of thecomposition comprising ethylenically unsaturated, bidentate phosphorusligands described in Example 1 were used to prepare catalyst accordingto Method A. The procedures described above were used to evaluate thehydrocyanation of butadiene, the isomerization of 2M3BN and thehydrocyanation of 3PN.

[0160] Aspect 10: Hydrocyanation of butadiene: Analysis showed that 87%of the starting HCN had been converted to useful nitriles, with a3-pentenenitrile to 2-methyl-3-butenenitrile ratio (3PN/2M3BN) of 1.13.

[0161] Aspect 10: Hydrocyanation of 3-pentenenitrile: GC analysis using2-ethoxyethyl ether as an internal standard showed 19.4% of the startingpentenitriles had been converted to dinitrile product (54% yield basedon HCN). The selectivity to the linear ADN isomer was 93.7%.

[0162] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: GC analysiswith valeronitrile as an internal standard showed 3PN/2M3BN ratio of1.1.

Example 2

[0163] Aspect 3: Polymerization of ethylenically unsaturated ligand (1):To 1.230 grams of the tacky brown solid produced in Example 1 was added10 mL of toluene and 20 milligrams of2,2′-azobis(2-methylpropanenitrile), sold by E. I. du Pont de Nemours &Co., Inc. as Vazo®64 free radical initiator. The mixture was heated to65° C. for two days and 70° C. for one additional day. Acetonitrile wasadded and the toluene solvent was removed under vacuum. To the residuewas added 30 mL of acetonitrile producing a yellow solid. Theacetonitrile solvent was decanted off and the residue dried under vacuum(³¹P NMR in CDCl₃: 141.43, 134.39, 134.30, 133.97, 133.48, 132.85, and131.21 and Elemental Analysis: 74.81%C; 6.99%H; 4.31%P).

Example 2A

[0164] Aspect 9: Preparation of catalyst: 50 mg (0.042 mmol) of thepolymer in Example 2 was used to prepare catalyst according to Method A.

[0165] The procedures described above were used to evaluate thehydrocyanation of BD, the isomerization of 2M3BN and the hydrocyanationof 3PN.

[0166] Aspect 10: Hydrocyanation of butadiene: Analysis showed that86.2% of the starting HCN had been converted to useful nitriles(3PN/2M3BN=1.6).

[0167] Aspect 10: Hydrocyanation of 3-pentenenitrile: GC analysis using2-ethoxyethyl ether as an internal standard showed 33.2% of the startingpentenitriles had been converted to dinitrile product (92% yield basedon HCN). The selectivity to the linear ADN isomer was 93.3%.

[0168] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: GC analysiswith valeronitrile as an internal standard indicated 3PN/2M3BN ratio of16.3.

Example 2B

[0169] Aspect 12: Hydroformylation of 3PN using the polymeric phosphitedescribed in Example 2: GC analysis indicated 34% conversion of 3PN to amixture containing the mono-aldehydes and valeronitrile; selectivity to5-formylvaleronitrile: 16% on a mole basis; linearity of aldehydesproduced: 19%.

Example 3

[0170] Aspect 3: Copolymerization of ethylenically unsaturated ligand(1) with methyl acrylate: To 0.760 grams of the tacky brown solid fromExample 1 was added 10 mL of toluene, 55 milligrams of methyl acrylateand 20 milligrams of Vazo®64 free radical initiator. The mixture washeated at 65° C. for 2 days and 70° C. for one additional day. Thetoluene solvent was removed under vacuum and 30 mL of acetonitrile wasadded. The acetonitrile solvent was decanted and the yellow solid driedunder vacuum (³¹P NMR in CDCl₃: 142.22, 135.21, 135.13, 134.78, 134.32,133.63, 132.04, and 131.30 and Elemental Analysis: 73.56%C; 7.09%H;4.61%P).

Example 3A

[0171] Aspect 9: Preparation of catalyst: 54 mg (0.042 mmol) of thepolymer in Example 3 was used to prepare catalyst according to Method A.

[0172] The procedures described above were used to evaluate thehydrocyanation of BD, the isomerization of 2M3BN and the hydrocyanationof 3PN.

[0173] Aspect 10: Hydrocyanation of butadiene: Analysis showed that86.1% of the starting HCN had been converted to useful nitriles(3PN/2M3BN=2.0).

[0174] Aspect 10: Hydrocyanation of 3-pentenenitrile: GC analysis using2-ethoxyethyl ether as an internal standard showed 32.7% of the startingpentenitriles had been converted to dinitrile product (90.3% yield basedon HCN). The selectivity to the linear ADN isomer was 93.3%.

[0175] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: GC analysiswith valeronitrile as an internal standard indicated 3PN/2M3BN ratio of15.6.

Example 3B

[0176] Aspect 12: Hydroformylation of 3PN with the polymeric phosphatedescribed in Example 3: GC analysis indicated 33% conversion of 3PN to amixture containing the mono-aldehydes and valeronitrile; selectivity to5-formylvaleronitrile: 31% on a mole basis; linearity of aldehydesproduced: 39%.

Example 4

[0177] Aspect 3: Copolymerization of ethylenically unsaturated ligand(1) with bisphenol A dimethacrylate: To 0.650 grams of the tacky brownsolid from Example 1 was added 10 mL of toluene and 199 milligrams ofbisphenol A dimethacrylate and 20 milligrams of Vazo®64 free radicalinitiator. The mixture was heated at 65° C. for 2 days and 70° C. forone additional day. The toluene solvent was removed under vacuum and 30mL of acetonitrile was added. The acetonitrile solvent was decanted andthe remaining polymeric yellow solid was dried under vacuum. The solidswells in CDCl₃ but appears insoluble.

[0178] Aspect 9: Preparation of catalyst: To 0.725 g of the above yellowsolid was added 4 mL of toluene. The mixture was stirred for 30 minutesand then 87 mg of Ni(COD)₂ and an additional 4 mL of toluene were added.The mixture was stirred for one hour before removing the solvent underreduced pressure.

Example 4A

[0179] Fourteen mg of the catalyst prepared in Example 4 was used foreach screen. The procedures described above were used to evaluate thehydrocyanation of BD, the isomerization of 2M3BN and the hydrocyanationof 3PN.

[0180] Aspect 10: Hydrocyanation of butadiene: Analysis showed that72.9% of the starting HCN had been converted to useful nitriles(3PN/2M3BN=7.78).

[0181] Aspect 10: Hydrocyanation of 3-Pentenenitrile: GC analysis using2-ethoxyethyl ether as an internal standard showed 30.3% of the startingpentenitriles had been converted to dinitrile product (84% yield basedon HCN). The selectivity to the linear ADN isomer was 94.0%.

[0182] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: GC analysiswith valeronitrile as an internal standard indicated 3PN/2M3BN ratio of15.2.

Example 5

[0183] Aspect 3: Copolymerization of ethylenically unsaturated ligand(1) with the diacrylate of 2,2-bis(4-hydroxy-3-methylphenyl)propane: To0.640 grams of the tacky brown solid from Example 1 was added 10 mL oftoluene, 0.196 grams of the diacrylate of2,2-bis(4-hydroxy-3-methylphenyl)propane and 20 milligrams of Vazo®64free radical initiator. The mixture was heated at 65° C. for 2 days and70° C. for one additional day. The toluene solvent was removed undervacuum and 30 mL of acetonitrile was added. The acetonitrile solvent wasdecanted and the yellow polymeric solid was dried under vacuum. Thesolid swells in CDCl₃ but appears insoluble.

[0184] Aspect 9: Preparation of catalyst: To 0.707 g of the solid fromExample 5 was added 4 mL of toluene. After stirring for 30 minutes, 85mg of Ni(COD)2 was added. An additional 4 mL of toluene was added andthe mixture was stirred for one hour. The solvent was removed undervacuum and the residue vacuum dried.

Example 5A

[0185] Fourteen mg of the catalyst prepared in Example 5 was used foreach screen. The procedures described above were used to evaluate thehydrocyanation of BD, the isomerization of 2M3BN and the hydrocyanationof 3PN.

[0186] Aspect 10: Hydrocyanation of butadiene: Analysis showed that80.4% of the starting HCN had been converted to useful nitriles(3PN/2M3BN=4.95).

[0187] Aspect 10: Hydrocyanation of 3-pentenenitrile: GC analysis using2-ethoxyethyl ether as an internal standard showed 31.3% of the startingpentenitriles had been converted to dinitrile product (86% yield basedon HCN). The selectivity to the linear ADN isomer was 94.5%.

[0188] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: GC analysiswith valeronitrile as an internal standard indicated 3PN/2M3BN ratio of15.5.

Example 5B

[0189] Aspect 12: Hydroformylation of 3PN with the polymeric phosphitedescribed in Example 5: GC analysis indicated 26% conversion of 3PN to amixture containing the mono-aldehydes and valeronitrile; selectivity to5-formylvaleronitrile: 34% on a mole basis; linearity of aldehydesproduced: 45%.

Example 6

[0190] Aspect 2: Preparation of ethylenically unsaturated ligand (6): Aflask with a magnetic stir bar was charged with 0.248 grams of thephosphorodichlorodite of o-cresol, 0.391 grams of the monoacrylate of2,2-bis(4-hydroxy-3-methylphenyl)propane (derived from the reaction ofacryloyl chloride with 2,2-bis(4-hydroxy-3-methylphenyl)propane) and 15mL of toluene). The mixture was cooled to −30° C. and a pre-cooledsolution of triethylamine (0.212 g) in 10 mL of toluene was added. Theslurry was stirred for 2 hours. ³¹P NMR of the solution: 162.91 (majorpeak) with minor peaks at 165.46 and 161.65. The mixture was cooled to−30° C. and 0.206 g of3,3′-diisopropyl-5,5′,6,6′-tetramethyl-2,2′-biphenol was added. Moretriethylamine was added (0.2 g). The mixture was stirred overnight andthen filtered and solvent removed to give 0.765 grams of tacky opaquesolid (³¹P NMR (CDCl₃): 135.45, 135.17, 135.13, 135.03, 132.84, 132.76,132.67, 132.56, 132.51, 132.45, 132.35, 132.27, 132.07, 131.98, 127.75,and 127.70).

Example 6A

[0191] Aspect 9: Preparation of catalyst: 51 mg (0.042 mmol) of thecomposition comprising monomeric bidentate phosphorus ligands in Example6 was used to prepare catalyst according to Method A.

[0192] The procedures described above were used to evaluate thehydrocyanation of BD, the isomerization of 2M3BN and the hydrocyanationof 3PN.

[0193] Aspect 10: Hydrocyanation of butadiene: Analysis showed that88.0% of the starting HCN had been converted to useful nitriles(3PN/2M3BN=0.87).

[0194] Aspect 10: Hydrocyanation of 3-pentenenitrile: GC analysis using2-ethoxyethyl ether as an internal standard showed 21.5% of the startingpentenitriles had been converted to dinitrile product (59% yield basedon HCN). The selectivity to the linear ADN isomer was 95.8%.

[0195] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: GC analysiswith valeronitrile as an internal standard indicated 3PN/2M3BN ratio of2.05.

Example 7

[0196] Aspect 3: Polymerization of ethylenically unsaturated ligand (6):To 0.700 grams of the tacky opaque solid produced in Example 6 was added10 mL of toluene. The mixture was cooled to −30° C. and 20 milligrams ofVazo®64 free radical initiator were added. The mixture was heated at 65°C. for two days and then 70° C. for one additional day. The toluenesolvent was removed in vacuum and 30 mL of acetonitrile was added. Theacetonitrile solution was decanted and the residue dried under vacuum togive a white solid (Elemental Analysis: 74.30% C; 7.35% H; 4.34% P).

Example 7A

[0197] Aspect 9: Preparation of catalyst: 51 mg (0.042 mmol) of thepolymer from Example 7 was used to prepare catalyst according to MethodA.

[0198] The procedures described above were used to evaluate thehydrocyanation of BD, the isomerization of 2M3BN and the hydrocyanationof 3PN.

[0199] Aspect 10: Hydrocyanation of butadiene: Analysis showed that86.1% of the starting HCN had been converted to useful nitriles(3PN/2M3BN=0.76).

[0200] Aspect 10: Hydrocyanation of 3-pentenenitrile: GC analysis using2-ethoxyethyl ether as an internal standard showed 32.6% of the startingpentenitriles had been converted to dinitrile product (90% yield basedon HCN). The selectivity to the linear ADN isomer was 89.0%.

[0201] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: GC analysiswith valeronitrile as an internal standard indicated 3PN/2M3BN ratio of16.5.

Example 7B

[0202] Aspect 12: Hydroformylation of 3-pentenenitrile with thepolymeric phosphite described in Example 7: GC analysis indicated 41%conversion of 3PN to a mixture containing the mono-aldehydes andvaleronitrile; selectivity to 5-formylvaleronitrile: 54% on a molebasis; linearity of aldehydes produced: 71%.

Example 8

[0203] Aspect 2: Preparation of ethylenically unsaturated ligand (8):Under nitrogen, a 100 mL flask with magnetic stir bar was charged with1.880 grams of 2,2-bis(4-hydroxy-3-methylphenyl)propane, 0.664 grams ofacryloyl chloride, and 40 mL of THF. The mixture was cooled to −30° C.and a pre-cooled solution (at −30° C.) containing 1 gram oftriethylamine in 15 mL of THF was added. The THF was removed undervacuum and the residue dissolved in 50 mL of THF. To this slurry wasadded 0.503 grams of phosphorus trichloride. The mixture was cooled to−30° C. and a pre-cooled solution containing 0.5 gram of triethylaminein 10 mL of THF was added. After stirring for several days, 0.598 gramsof 3,3′-diisopropyl-5,5′,6,6′-tetramethyl-2,2′-biphenol was added alongwith 1.2 grams of triethylamine. The mixture was stirred for fortyminutes, filtered and the solvent was removed under vacuum to give 3.146grams of a yellow solid (³¹P NMR (CDCl₃): 135.58, 135.25, 135.18,134.80, 134.71, 132.71, 131.90, 130.80, 127.94, and 127.87).

Example 8A

[0204] Aspect 9: Preparation of catalyst: 68 mg (0.042 mmol) of thecomposition comprising monomeric bidentate phosphorus ligands in Example8 was used to prepare catalyst according to Method A. The proceduresdescribed above were used to evaluate the hydrocyanation of BD, theisomerization of 2M3BN and the hydrocyanation of 3PN.

[0205] Aspect 10: Hydrocyanation of butadiene: Analysis showed that84.8% of the starting HCN had been converted to useful nitriles(3PN/2M3BN=0.51).

[0206] Aspect 10: Hydrocyanation of 3-pentenenitrile: GC analysis using2-ethoxyethyl ether as an internal standard showed 31.0% of the startingpentenitriles had been converted to dinitrile product (86% yield basedon HCN). The selectivity to the linear ADN isomer was 92.8%.

[0207] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: GC analysiswith valeronitrile as an internal standard indicated 3PN/2M3BN ratio of2.0.

Example 9

[0208] Aspect 3: Polymerization of ethylenically unsaturated ligand (8):To 0.700 grams of the monomeric yellow solid from Example 8 was added 1mL of toluene and 20 milligrams of Vazo®64 free radical initiator, and0.2 mL of THF. The mixture was heated at 70° C. for one day. Solvent wasremoved and the yellow polymerized solid was collected.

[0209] Aspect 9: Preparation of nickel catalyst: To 565 milligrams ofthe above polymeric solid was added 2 mL of toluene and 64 milligrams ofNi(COD)₂. Another 1 mL of toluene was added and the slurry was stirredfor 2 hours. The mixture was stored overnight in a −30° C. freezer andthen the toluene solvent was decanted and the solid vacuum dried.

Example 9A

[0210] Fifteen mg of catalyst from Example 9 was used for each screen.The procedures described above were used to evaluate the hydrocyanationof BD, the isomerization of 2M3BN and the hydrocyanation of 3PN.

[0211] Aspect 10: Hydrocyanation of butadiene: Analysis showed that75.0% of the starting HCN had been converted to useful nitriles(3PN/2M3BN=2.35).

[0212] Aspect 10: Hydrocyanation of 3-pentenenitrile: GC analysis using2-ethoxyethyl ether as an internal standard showed 30.9% of the startingpentenitriles had been converted to dinitrile product (85% yield basedon HCN). The selectivity to the linear ADN isomer was 92.2%.

[0213] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: GC analysiswith valeronitrile as an internal standard indicated 3PN/2M3BN ratio of15.8.

Example 10

[0214] Aspect 3: Copolymerization of ethylenically unsaturated ligand(8) with methyl acrylate: To 0.600 grams of the yellow solid fromExample 8 was added 1 mL of toluene, 0.032 grams of methyl acrylate, 20milligrams of Vazo®64 free radical initiator, and 0.2 mL of THF. Themixture was heated at 70° C. for one day. The toluene solvent wasremoved and the yellow solid was collected.

[0215] Aspect 9: Preparation of nickel catalyst: To 550 milligrams ofthe above solid was added 3 mL of toluene and the mixture was stirredfor 30 minutes. To this mixture was added 59 milligrams of Ni(COD)₂. Theresulting red slurry was stirred for 45 minutes, the toluene solvent wasremoved under vacuum, and the remaining solid was vacuum dried.

Example 10A

[0216] Fifteen mg of the catalyst from Example 10 was used for eachscreen. The procedures described above were used to evaluate thehydrocyanation of BD, the isomerization of 2M3BN, and the hydrocyanationof 3PN.

[0217] Aspect 10: Hydrocyanation of butadiene: Analysis showed that70.6% of the starting HCN had been converted to useful nitriles(3PN/2M3BN=2.58).

[0218] Aspect 10: Hydrocyanation of 3-pentenenitrile: GC analysis using2-ethoxyethyl ether as an internal standard showed 30.6% of the startingpentenitriles had been converted to dinitrile product (85% yield basedon HCN). The selectivity to the linear ADN isomer was 92.3%.

[0219] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: GC analysiswith valeronitrile as an internal standard indicated 3PN/2M3BN ratio of15.2.

Example 11

[0220] Aspect 3: Copolymerization of ethylenically unsaturated ligand(8) with bisphenol A dimethacrylate: To 0.600 grams of the yellow solidfrom Example 8 was added 1 mL of toluene, 0.134 grams of bisphenol Adimethacrylate, 20 milligrams of Vazo®64 free radical initiator, and 0.2mL of THF. The mixture was heated at 70° C. for one day. The THF solventwas removed and the yellow solid was collected.

[0221] Aspect 9: Preparation of nickel catalyst: To 675 milligrams ofthe above solid was added 3 mL of toluene and the mixture was stirredfor 30 minutes. To this mixture was added 62 milligrams of Ni(COD)₂. Thered slurry was stirred for 30 minutes, the toluene solvent was removedunder vacuum, and the solid was vacuum dried.

Example 11A

[0222] Eighteen mg of the catalyst from Example 11 was used for eachscreen. The procedures described above were used to evaluate thehydrocyanation of BD, the isomerization of 2M3BN, and the hydrocyanationof 3PN.

[0223] Aspect 10: Hydrocyanation of butadiene: Analysis showed that75.3% of the starting HCN had been converted to useful nitriles(3PN/2M3BN=3.04).

[0224] Aspect 10: Hydrocyanation of 3-pentenenitrile: GC analysis using2-ethoxyethyl ether as an internal standard showed 30.3% of the startingpentenitriles had been converted to dinitrile product (84% yield basedon HCN). The selectivity to the linear ADN isomer was 91.5%.

[0225] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: GC analysiswith valeronitrile as an internal standard indicated 3PN/2M3BN ratio of15.9.

Example 11B

[0226] Aspect 10: Semibatch 3-pentenenitrile hydrocyanation using nickelcatalyst: A reaction mixture of 0.567 grams of the above catalyst, 0.027grams of zinc chloride, 5 mL of toluene and 5 mL of 3PN in a closedreactor was placed in a 50° C. oil bath and HCN saturated nitrogen wasdelivered at a nitrogen flow rate of 24 cc/min. The reaction was heatedat 50° C. for 1 hour and then at 70° C. for 30 minutes. Nitrogen flowwas decreased to 12 cc/min. and the reaction was run at 70° C. for anadditional 90 minutes. The temperature was then increased to 80° C. andthe reaction was continued for another 90 minutes. GC analysis indicated68% conversion of 3-pentenenitrile to dinitrile with an ADN selectivityof 89%.

Example 12

[0227] Aspect 2: Preparation of ethylenically unsaturated ligand (12):Under nitrogen, a 100 mL flask with magnetic stir bar was charged with0.931 grams of the monoacrylate of2,2-bis(4-hydroxy-3-methylphenyl)propane (prepared from the reaction ofacryloyl chloride with 2,2-bis(4-hydroxy-3-methylphenyl)propane), 0.627grams of the phosphorodichloridite of o-cresol, and 40 mL of toluene.The mixture was cooled to −30° C. and a precooled solution (at −30° C.)containing 0.4 grams of triethylamine in 15 mL of toluene was added.After stirring for 2 hours, ³¹P NMR in CDCl₃ indicated a peak at 162.8ppm. The mixture was cooled to −30° C. and 0.448 grams of3,3′,4,4′,5,5′-hexamethyl-2,2′-biphenol and 0.65 grams of triethylaminein 2 mL of THF were added. After stirring overnight, the mixture wasfiltered and the THF removed under vacuum to give a yellow solid. Thesolid was dissolved in 10 mL of toluene and 0.8 grams of triethylaminewas added in 5 mL of THF. The mixture was stirred overnight andfiltered. The solvent was removed. ³¹P NMR indicated somephosphorodichloridite still present. The residue was dissolved in THFand 0.75 grams of triethylamine were added. After stirring overnight,the mixture was filtered through silica gel, and the solvent was removedunder vacuum. 1.225 Grams of yellow solid were recovered (³¹P NMR inCDCl₃: 137.47, 137.31, 135.29, 135.21, 135.15, 135.00, 134.82, 134.73,134.40, 134.31, 133.41, 133.40, 132.07, 131.98, 130.44, 127.74, and127.69).

Example 12A

[0228] Aspect 9: Preparation of catalyst: 50 mg (0.042 mmol) of thecomposition comprising monomeric bidentate phosphorus ligands preparedas in Example 12 were used to prepare catalyst according to Method A.

[0229] The procedures described above were used to evaluate thehydrocyanation of BD, the isomerization of 2M3BN, and the hydrocyanationof 3PN.

[0230] Aspect 10: Hydrocyanation of butadiene: Analysis showed that80.0% of the starting HCN had been converted to useful nitriles(3PN/2M3BN=0.95).

[0231] Aspect 10: Hydrocyanation of 3-pentenenitrile: GC analysis using2-ethoxyethyl ether as an internal standard showed 26.8% of the startingpentenitriles had been converted to dinitrile product (74% yield basedon HCN). The selectivity to the linear ADN isomer was 95.5%.

[0232] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: GC analysiswith valeronitrile as an internal standard indicated 3PN/2M3BN ratio of4.0.

Example 12B

[0233] Aspect 3: Polymerization of ethylenically unsaturated ligand(12): To 0.657 grams of the yellow monomeric solid produced in Example12 was added 0.9 mL of toluene, 100 mL of THF and 20 milligrams ofVazo®64 free radical initiator. The mixture was heated at 70° C. for oneday. Solvent was removed and the yellow polymeric solid was collected.

[0234] Aspect 9: Preparation of nickel catalyst: To 375 milligrams ofthe above polymeric solid was added 5 mL of toluene and 58 milligram ofNi(COD)₂. The mixture was stirred overnight.

[0235] Aspect 10: Hydrocyanation of 3-pentenenitrile: 29 milligrams ofZnCl₂ and 5 mL of 3PN were added to the mixture. The mixture was heatedin a 50° C. oil bath and HCN was delivered with 24 cc/min. nitrogen flowrate. After 90 minutes of reaction, GC analysis indicated 57.6%conversion of 3PN with 92% selectivity to ADN. To the mixture was added5 mL of 3PN and the reaction was continued for 90 minutes. At thispoint, HCN delivery was stopped but the reaction was allowed to continueat 50° C. for 120 minutes. The mixture was allowed to sit under nitrogenat room temperature overnight. GC analysis indicated 62% conversion of3PN with 91.3% selectivity to ADN.

[0236] Ligand recycle: At this time, the solvent was removed via syringefrom the reactor. 5 mL of toluene, 5 mL of 3PN and 29 milligrams ofZnCl₂ were added to begin an additional reaction. The reaction wasplaced in a 70° C. oil bath and HCN was delivered with a nitrogen flowrate of 30 cc/min. The reaction was then stored at room temperatureovernight. The mixture was then heated at 70° C. oil bath with HCNdelivered with a nitrogen flow rate of 30 cc/min for 30 minutes. GCanalysis indicated 75% conversion of 3PN with selectivity to ADN of92.2%. To this mixture was added 5 mL of 3PN. The mixture was heated at70° C. oil bath with HCN delivered with a nitrogen flow rate of 30cc/min for 210 minutes. GC analysis indicated 65% conversion of 3PN withselectivity to ADN of 91.8%.

Example 12C

[0237] Aspect 9: Preparation of nickel catalyst: To 179 mg of the solidfrom the polymer prepared as in Example 12B was added 15 mL of THF. Themixture was stirred overnight and then 27.5 mg of Ni(COD)₂ was added.The solvent was removed under vacuum and the residue was vacuum dried.

[0238] Eleven mg of the catalyst from above was used for each screen.The procedures described above were used to evaluate the hydrocyanationof BD and the isomerization of 2M3BN.

[0239] Aspect 10: Hydrocyanation of butadiene: Analysis showed that 54%of the starting HCN had been converted to useful nitriles(3PN/2M3BN=1.1).

[0240] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: GC analysiswith valeronitrile as an internal standard indicated 3PN/2M3BN ratio of18.5.

Example 13

[0241] Preparation of 6,6′-divinyl-2,2′-dihydroxy-1,1′-binaphthyl:

[0242] A solution of 6,6′-dibromo-2,2′-dihydroxy-1,1′-binaphthyl (0.694g, 1.56 mmol), Pd(OAc)₂ (0.020 g, 5 mol %), P(o-tolyl)₃ (0.080 g, 15 mol%) and Et₃N (0.5 mL) in DMF (2 mL) was pressurized with ethylene (200psi) at 75° C. for 18 hrs. The resulting mixture was diluted in ethylacetate (20 mL) and filtered through celite, followed by water (20 mL)and brine (20 mL) washes. The solution was dried over MgSO₄ andevaporated to produce a tan solid, which was purified by columnchromatography to yield the desired product in 54% yield (0.286 g).

[0243] Aspect 2: Preparation of the diphosphite ligand (13): Under anatmosphere of nitrogen, a cold (−30° C.) Et₂O (5 mL) solution of6,6′-divinyl-2,2′-dihydroxy-1,1′-binaphthyl (0.051 g, 1.5×10⁻⁴ mol) andEt₃N (0.040, 3.9×10⁻⁴ mol) was slowly added to a Et₂O (5 mL) solution ofphosphorochlorodite of 2-isopropoxyphenol (0.140 g, 3.9×10⁻⁴ mol). Thesolution was allowed to warm up to room temperature and was stirred forone hour. The reaction mixture was filtered through celite and alumina.The volatiles were evaporated to yield a white powder in 67% yield.(0.100 g).

Example 13A

[0244] Aspect 3: Polymerization of the ethylenically unsaturatedcompound (13) with divinylbenzene: Under an atmosphere of nitrogen, avial fitted with a Teflon® fluoropolymer resin screwcap was charged withthe diphosphite (0.027 g, 2.7×10⁻⁵ mol) described in example 13, AIBN(0.002 g), DVB (0.1900 g) and THF (0.184 g). This vial was screwed shutand placed in a 70° C. oil bath for 24 hours. After polymerization, thepolymer was crushed and the volatiles were removed under vacuum. Theresulting white polymer (0.350 g) was insoluble in all organic solvents.Elemental analysis: P found: 1.51%.

[0245] Aspect 9: Preparation of nickel catalyst. A mixture of toluene (1mL) and Ni(COD)₂ (0.020 g) was added to the above polymer. The whitepolymer immediately turned yellow-orange. After stirring approximatelyone minute, the solution was filtered from the loaded polymer. Theyellow-orange polymer was rinsed with THF (2×3 mL) and dried undervacuum.

[0246] Aspect 10: Hydrocyanation of 3-pentenenitrile: A sample (0.052 gpolymer, 0.042 mmol diphosphite) was evaluated for hydrocyanation of 3PNusing the procedure described above. GC analysis using 2-ethoxyethylether as an internal standard showed 27.5% of the starting pentenitrileshad been converted to dinitrile product (76% yield based on HCN). Theselectivity to the linear ADN isomer was 92.1%.

Example 14

[0247] Aspect 2: Preparation of ethylenically unsaturated diphosphiteligand (14): Under an atmosphere of nitrogen, a cold (−30° C.) Et₂O (5mL) solution of3,3′,4,4′,5,5′,6,6′-octamethyl-2,2′-dihydroxy-1,1′-biphenyl (0.100 g,0.67 mmol) and Et₃N (0.152 g, 1.5 mmol) was slowly added to an Et₂O (5mL) solution of phosphorochlorodite oftrans-2-ethoxy-5-(1-propenyl)phenol (0.631 g, 1.5 mmol). The solutionwas allowed to warm to room temperature and was stirred for one hour.The reaction mixture was filtered through celite and alumina. Thevolatiles were evaporated to give 86% yield of a white powder (0.623 g).

Example 14A

[0248] Aspect 3: Polymerization of the ethylenically unsaturatedcompound (14) with divinylbenzene and styrene: Under an atmosphere ofnitrogen, a vial fitted with a Teflon® fluoropolymer resin screwcap wascharged with the diphosphite (0.100 g, 0.09 mmol) described in example14, AIBN (0.005 g), DVB (0.40 g), styrene (0.70 g) and THF (1.5 mL).This vial was screwed shut and placed in a 70° C. oil bath for 48 hours,after which DVB (0.75 g) and AIBN (0.005 g) were added and the vial wasreturned to the oil bath. After 48 hours, the opaque polymer was crushedand the volatiles were removed under vacuum. The resulting white polymer(0.137 g) was insoluble in all organic solvents.

[0249] Aspect 9: Preparation of nickel catalyst: A mixture of toluene (1mL) and Ni(oTTP)₃ (0.112 g) was added to the above polymer. The whitepolymer immediately turned yellow-orange. After stirring approximatelyone minute, the solution was filtered from the loaded polymer. Theyellow-orange polymer was rinsed with THF (2×3 mL) and dried undervacuum.

Example 14B

[0250] Aspect 8: Hydrocyanation of butadiene: A solution of HCN wasprepared by mixing 5 g of HCN with 15 g of valeronitrile. A butadienesolution was prepared by mixing 2 g of butadiene with 6 g of toluene. To30 mg of the nickel catalyst prepared in example 14A was added 0.28 mLof the butadiene solution and 0.12 mL of the HCN solution. The mixturewas heated at 80° C. for 3 hours. GC analysis indicated 81%3-pentenenitrile and 5.7% 2-methyl-3-butenenitrile.

Example 15

[0251] Aspect 5.1: Polymerization of6,6′-divinyl-2,2′-dihydroxy-1,1′-binaphthyl with styrene: Under nitrogenatmosphere, a vial fitted with a Teflon® fluoropolymer resin screwcapwas charged with 6,6′-divinyl-2,2′-dihydroxy-1,1′-binaphthyl (0.500g,1.48 mmol), AIBN (0.040 g), styrene (4.0 mL) and THF (4.0 mL). The vialwas screwed shut and placed in a 70° C. oil bath for 24 hours. Afterpolymerization, the polymer was crushed and the volatiles were removedunder vacuum. The resulting white polymer (4.8 g) was insoluble in allorganic solvents.

Example 16

[0252] Aspect 5.2: Formation of the diphosphite ligand from thepolymeric precursor of Example 15: Under nitrogen atmosphere, a coldsolution (−30° C.) of o-cresol (0.027 g, 0.25 mmol) in toluene (5 mL)was added to a solution of the phosphorodichlorodite of phenol (0.045 g,0.25 mmol) and n-Bu₃N (0.047 g, 0.25 mmol) in toluene (5 mL). Theresulting mixture was allowed to stir at room temperature for 1.5 hours,after which it was cooled to −30° C. This cold solution was added to acold slurry of polymer from example 15 (0.328 g, 0.10 mmol) and n-Bu₃N(0.047 g, 0.25 mmol) in toluene (5 mL). This mixture was stirred at roomtemperature for five hours. The polymer product was isolated byfiltration and washed with toluene and acetonitrile. After drying undervacuum, a tacky solid (0.350 g) was obtained.

[0253] Aspect 9: Preparation of nickel catalyst: This polymer (0.186 g)was mixed with toluene (3 mL) and cooled (−30° C.) for 30 minutes, afterwhich a cold solution of Ni(oTTP)₃ (0.055 g) in toluene (3 mL) was addedand allowed to stir at room temperature for 20 minutes. The resultingyellow-orange solid (0.140 g) was isolated by filtration and dried undervacuum.

Example 16A

[0254] Aspect 10: Hydrocyanation of BD with nickel catalyst prepared inExample 16: A solution of HCN was prepared by mixing 5 g of HCN with 15g of valeronitrile. A butadiene solution was prepared by mixing 2 g ofbutadiene with 6 g of toluene. To 44 mg of the nickel catalyst preparedin example 16 was added 0.28 mL of the butadiene solution and 0.12 mL ofthe HCN solution. The mixture was heated at 80° C. for 2 hours. GCanalysis indicated 8% 3-pentenenitrile and 5% 2-methyl-3-butenenitrile.

Example 17

[0255] Aspect 2: Preparation of ethylenically unsaturated,phosphorus-containing bidentate ligand (17): A 500 mL flask with amagnetic stirbar was charged with 8.500 g of2,2-bis(4-hydroxy-3-methylphenyl)propane and 3.001 g of acryloylchloride in 120 mL of THF. A solution of triethylamine (3.542 g) in 30mL of THF was added to the colorless solution dropwise over 60 minutes.The slurry was stirred at room temperature for four hours. Based on peakarea, GC on a DB5 column indicated 22% starting diol, 51% monoacrylateand 25% diacrylate. The mixture was cooled to −30° C., and 1.821 g ofphosphorus trichloride and 1.386 g of the phosphorochloridite ofo-cresol in 10 mL of THF were added. A precooled solution (−30° C.) oftriethylamine in 30 mL of THF was added to this mixture dropwise oversixty minutes. After stirring the mixture at room temperature for twohours, ³¹P NMR indicated major peaks at 161.96 and 161.77 with minorpeaks at 182.44, 131.04 and 126.71. The slurry was cooled back to −30°C. and 3.248 g of3,3′-diisopropyl-5,5′,6,6′-tetramethyl-2,2′-dihydroxy-1,1′-biphenyl and3.2 g of triethylamine were added. The mixture was stirred at roomtemperature for 2.5 hours. ³¹P NMR indicated a major peak at 131.82 andminor peaks at 134.62, 134.50, 134.23, 131.08 and 130.99. The slurry wasfiltered through celite, washed with THF, and the solvent was removed byvacuum. The residue was vacuum dried to give 14.866 g of off-whitesolid. Elemental analysis: 3.70%P.

Example 17A

[0256] Aspect 9: Preparation of catalyst. 7 mL of toluene and 110 g ofNi(COD)₂ were added to 1.000 g of the solid from Example 17. The mixturewas stirred for an hour and the solvent was removed by vacuum.

Example 17B

[0257] Aspect 3: Polymerization of nickel catalyst: To the residue fromExample 17A was added 1.0 mL of toluene and 20 mg of Vazo 64 freeradical initiator. The mixture was heated at 60° C. overnight. The hardyellow solid was crushed and heated at 60° C. for another two hours. Thesolvent was removed by vacuum and 10 mL of acetonitrile was added to theresidue. After stirring for 25 minutes, the solid was filtered, washedwith acetonitrile and diethyl ether and vacuum dried to give 1.048 g ofyellow solid.

Example 17C

[0258] Aspect 10: Hydrocyanation of butadiene: To 13 mg of the catalystfrom example 17B was added 1.045 mL of a solution containing butadieneand HCN. The solution was prepared by mixing 6.734 g valeronitrile,6.572 g 3-pentenenitrile, 5.476 g butadiene, and 2.187 g of HCN. Themixture was heated at 80° C. for 2 hours. GC indicated 38% conversion tonitriles with 3PN/2M3BN of 0.53.

Example 17D

[0259] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: To 13 mg ofthe catalyst from Example 17B was added 0.266 mL of 2M3BN invaleronitrile solution (prepared by mixing 20.7 g 2M3BN and 1.8 g ofvaleronitrile). The mixture was heated at 80° C. for 2 hours and thenheated at 100° C. for one hour. GC indicated 3PN/2M3BN of 0.6.

Example 18

[0260] Aspect 2: Preparation of ethylenically unsaturated,phosphorus-containing bidentate ligand (18): A mixture containingbidentate phosphite was prepared similarly to that of Example 17. A 500ml flask was charged with a stir bar, 8.204 g of2,2-bis(4-hydroxy-3-methylphenyl)propane, 2.896 g of acryloyl chlorideand 175 mL of THF. The mixture was cooled to −30 C. and then a precooledsolution (−30 C.) of triethylamine (3.490 g) in 50 mL of THF was addeddropwise over 40 minutes. The slurry was warmed to room temperature andstirred for 90 minutes. Based on peak area, GC indicated 26% startingdiol, 45% monoacrylate and 26% diacrylate. The mixture was filteredthrough celite and washed with THF. The solution was concentrated to 160mL by removing solvent under vacuum. To 40 mL of this solution was added440 mg of phosphorus trichloride and 334 mg of the phosphorochloriditeof o-cresol in 10 mL of THF. The mixture was cooled to −30 C. and aprecooled solution (−30 C.) of triethylamine (950 mg) in 10 mL of THFwas added. The mixture was stirred at room temperature for 30 minutes.To this mixture was added 784 mg of3,3′-diisopropyl-5,5′,6,6′-tetramethyl-2,2′-dihydroxy-1,1′-biphenyl.and1.2 g triethylamine. The mixture was stirred overnight. ³¹P NMRindicated peaks at 135.07, 135.01, 134.90, 132.23, 131.48, 131.38 ppm.The slurry was filtered through celite, washed with THF, the solvent wasremoved by vacuum and the solid was dried under vacuum. A tan solid(3.473 g) was obtained.

Example 18A

[0261] Aspect 3: Polymerization of ethylenically unsaturated ligand(18): The solid was dissolved in 6 mL of toluene and 30 mg of Vazo 64free radical initiator. The mixture was heated at 50° C. for six hoursand then held at 60° C. overnight. The solid was crushed and heated at70° C. for three hours. The solvent was removed by vacuum and the solidwas filtered, washed with diethyl ether and vacuum dried to give 3.483 gof yellow solid. Elemental analysis: 3.72% P.

Example 18B

[0262] Aspect 9: Preparation of catalyst: The nickel catalyst wasprepared from the polymeric ligand described in Example 18A. To 3.28 gof the polymer ligand was added 43 mL of THF. The mixture was stirredovernight and then 361 mg of Ni(COD)₂ was added. The mixture was stirredfor one hour and the solid was vacuum dried for 3.5 hours and 20 mL of3PN added. The solid was filtered and washed with 3PN, and acetonitrileand vacuum dried to give 3.170 g of yellow solid.

Example 18C

[0263] Aspect 10: Hydrocyanation of butaediene: To 15 mg of the catalystprepared in Example 18B were added 0.280 mL of a solution containingbutadiene (prepared by mixing 6.8 g toluene and 2.0 g butadiene) and0.120 mL of a solution containing HCN (prepared by mixing 5 g HCN and 15g of valeronitrile). The mixture was heated at 80° C. for 2 hours. GCanalysis indicated 69% conversion to nitriles with a 3PN/2M3BN of 28.

Example 18D

[0264] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: To 15 mg ofthe catalyst prepared in example 18B was added 0.266 mL of a solution of2M3BN in valeronitrile (prepared by mixing 20.7 g 2M3BN and 1.8g ofvaleronitrile). The mixture was heated to 100 C. for one hour. GCindicated 3PN/2M3BN ratio of 20.1.

Example 18E

[0265] Aspect 10: Semi-batch hydrocyanation of 3-pentenenitrile: To0.388 g of the catalyst from Example 18B was added 19 mg of zincchloride and 5 mL of 3PN. The mixture was heated in a 70 C. oil bath andHCN was delivered with 12 cc/min. nitrogen flow rate. After 180 minutes,GC indicated 93.9% conversion to dinitrile with ADN selectivity of88.4%.

Example 19

[0266] Aspect 7: Preparation of polymeric phosphorochloridite: A 200 mLround bottom flask was charged with 8.716 g of2,2-bis(4-hydroxy-3-methylphenyl)propane, 3.077 g of acryloyl chloride,and 80 mL of THF. The mixture was cooled to −30° C. and a precooled(−30° C.) solution of triethylamine (3.643 g) in 20 mL of THF was added.The mixture was stirred at room temperature for 45 minutes and thencooled back to −30° C. To this mixture was added 7.106 g of thephosphorodichloridite of o-cresol in 20 mL of THF and then a precooledsolution (−30° C.) of triethylamine (3.9 g) in 25 mL of THF. Afterstirring at room temperature for 45 minutes, ³¹P NMR indicated peaks at157.16 and 157.14 ppm and small peaks at 126.73 and 126.46 ppm. Thesolution was filtered and the total volume was adjusted to 150 mL byaddition of THF.

[0267] The solvent from 10 mL of the solution was removed by vacuum andthe residue was vacuum dried. The residue was dissolved in 0.5 mL oftoluene and 10 mg of Vazo 64 free radical initiator was added. Themixture was heated at 70° C. for 3 hours. The solid was crushed andheated at 70° C. for another hour. The toluene was removed by vacuum andthe solid was vacuum dried overnight. The solid was washed with diethylether and dried under vacuum to give 807 mg of brown solid.

Example 19A

[0268] Aspect 7: Polymerization of Polymeric Phosphite:

[0269] A vial was charged with 0.750g of the polymericphosphorochloridite prepared in Example 19, 210 mg of3,3′,5,5′,6,6′-hexamethyl-2,2′-dihydroxy-1,1′-biphenyl and 10 mL of THF.To this mixture was added 0.800 g of tri(n-butylamine) and the mixturewas stirred overnight. The solvent was removed by vacuum andacetonitrile was added. The solid was filtered and washed withacetonitrile to give 770 mg of pale beige solid. Elemental analysis:3.16%P.

Example 19B

[0270] Aspect 9: Preparation of catalyst: To 0.560 g of the polymericphosphite prepared in Example 19A was added 5 mL of THF. The mixture wasstirred overnight and another 1 mL of THF was added. To the mixture wasadded 0.052 g of Ni(COD)₂, giving an orange slurry. After stirring atroom temperature for four hours, the solvent was removed by vacuum andthe residue vacuum dried for three hours. To the residue was added 5 mLof 3PN and the solid was filtered, washed successively withacetonitrile, 3PN, and acetonitrile, vacuum dried to give 593 mg oforange solid.

Example 19C

[0271] Aspect 10: Hydrocyanation of butadiene: To 16 mg of catalystprepared as described in Example 19B was added 1.045 mL of a solutioncontaining butadiene and HCN (prepared by mixing 6.734 g ofvaleronitrile, 6.572 g of 3-pentenenitrile, 5.476 g of butadiene, and2.187 g of HCN). The mixture was heated at 80° C. for 2 hours. GCindicated 82% conversion to nitriles with 3PN/2M3BN of 1.9.

Example 19D

[0272] Aspect 11: Isomerization of 2-methyl-3-butenenitrile: To 16 mg ofcatalyst prepared as described in Example 19C was added 0.266 mL of asolution containing 2M3BN in valeronitrile (prepared by mixing 20.7 g2M3BN and 1.8 g of valeronitrile). The mixture was heated to 100° C. forone hour. GC indicated 3PN/2M3BN ratio of 10.1.

[0273] Having thus described and exemplified the invention with acertain degree of particularity, it should be appreciated that thefollowing claims are not to be so limited but are to be afforded a scopecommensurate with the wording of each element of the claim andequivalents thereof.

What is claimed is:
 1. A phosphorus-containing, bidentate ligand monomercompound of the Formula I or of the Formula II,

wherein: x=0 to 4; y=0 to 2; a and b are individually either 0, 1, or 2,provided a+b=2; each Ar is individually selected from the groupconsisting of phenyl, substituted phenyl, naphthyl, and substitutednaphthyl, provided that the two Ar groups that are directly orindirectly bonded to the same phosphorus atom may be linked to eachother by a linking unit selected from the group consisting of directbond, alkylidene, secondary or tertiary amine, oxygen, sulfide, sulfone,and sulfoxide; each Ar can be further substituted with C₁ to C₂₀branched or straight chain alkyl, C₁ to C₂₀ cycloalkyl, C₆ to C₂₀ aryl,acetal, ketal, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine,chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl,hydrocarbylsulfonyl, hydrocarbylcarbonyl or cyclic ether; each R isindividually selected from the group consisting of hydrogen, ethenyl,propenyl, acryloyl, methacryloyl and an organic radical with a terminalethenyl, propenyl, acryloyl, or methacryloyl group; each R″ isindividually selected from the group consisting of hydrogen, linear orbranched alkyl, cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy,aryloxy, formyl, ester, fluorine, chlorine, bromine, perhaloalkyl,hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarbylcarbonyl, cyclicether, ethenyl, propenyl, and an organic radical with a terminal ethenylor propenyl group; provided at least one R represents ethenyl, propenyl,acryloyl, methacryloyl or the organic radical with a terminal ethenyl,propenyl, acryloyl, or methacryloyl group or at least one R″ representsethenyl, propenyl, or the organic radical with a terminal ethenyl orpropenyl group.
 2. A compound of claim 1, Formula I, wherein a=2, b=0, Ris primary or secondary alkyl located ortho to the oxygen bonded to Ar,wherein y≧1, and wherein at least one R″ is primary or secondary alkylgroup and is located at the ortho position of the oxygen bonded to thebinaphthalene group, or a compound of claim 1, Formula II wherein a=2,b=0, R is primary or secondary alkyl located ortho to the oxygen bondedto Ar, wherein x≧1 and wherein at least one R″ is primary or secondaryalkyl group and is located at the ortho positions of the oxygen bondedto the biphenylene group.
 3. A process for preparing compositionscomprising phosphorus-containing, bidentate ligand (monomer) compoundsof Formula I, wherein a is 1 or 2 and b is 0 or 1 with the conditionthat a+b=2, or compounds of Formula II, wherein a is 1 or 2 and b is 0or 1 with the condition that a+b=2,

wherein: x=0 to 4; y=0 to 2; each Ar is individually selected from thegroup consisting of phenyl, substituted phenyl, naphthyl, andsubstituted naphthyl, provided that the two Ar groups that are directlyor indirectly bonded to the same phosphorus atom may be linked to eachother by a linking unit selected from the group consisting of directbond, alkylidene, secondary or tertiary amine, oxygen, sulfide, sulfone,and sulfoxide; each R″ is individually selected from the groupconsisting of hydrogen, linear or branched alkyl, cycloalkyl, acetal,ketal, aryl, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine,chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl,hydrocarbylsulfonyl, hydrocarbylcarbonyl, cyclic ether, ethenyl,propenyl, and an organic radical with a terminal ethenyl or propenyl;each R is individually selected from the group consisting of hydrogen,acryloyl, methacryloyl and an organic radical with a terminal acryloyl,or methacryloyl group; provided at least one R is acryloyl ormethacryloyl or an organic radical with a terminal acryloyl ormethacryloyl group, said process comprising: (1) reacting at least oneof acryloyl chloride or methacryloyl chloride with a polyhydric alcoholto make at least one of monoacrylate or monomethacrylate, (2) reactingat least one of monoacrylate or monomethacrylate with at least one ofphosphorus trichloride or phosphorodichloridite or aryldichlorophosphine(Cl₂P—Ar) to give at least one phosphorochloridite- oraryl,aryloxychlorophosphinite-containing acrylate or methacrylate, (3)reacting at least one phosphorochloridite- oraryl,aryloxychlorophosphinite-containing acrylate and/or methacrylatefrom step (2) with at least one compound of Formula III and/or at leastone compound of Formula IV,

wherein: each R′ individually is hydrogen or M, wherein M is an alkalimetal or an alkaline earth metal.
 4. A compound of claim 3, Formula III,wherein a=2, b=0, R is primary or secondary alkyl located ortho to theoxygen bonded to Ar, wherein y≧1, and wherein at least one R″ is primaryor secondary alkyl group and is located at the ortho position of theoxygen bonded to the binaphthalene group, or a compound of claim 2,Formula IV wherein a=2, b=0, R is primary or secondary alkyl locatedortho to the oxygen bonded to Ar, wherein x≧1 and wherein at least oneR″ is primary or secondary alkyl group and is located at the orthopositions of the oxygen bonded to the biphenylene group.
 5. A method formaking a polymeric, phosphorus-containing composition by heating, in thepresence of an initiator, and, optionally in the presence of a GroupVIII transition metal, a composition comprising at least one compound ofFormula I and/or at least one compound of Formula II,

wherein: x=0 to 4; y=0 to 2; a and b are individually either 0, 1, or 2,provided a+b=2; each Ar is individually selected from the groupconsisting of phenyl, substituted phenyl, naphthyl, and substitutednaphthyl, provided that the two Ar groups that are directly orindirectly bonded to the same phosphorus atom may be linked to eachother by a linking unit selected from the group consisting of directbond, alkylidene, secondary or tertiary amine, oxygen, sulfide, sulfone,and sulfoxide; each Ar can be further substituted with C₁ to C₂₀branched or straight chain alkyl, C₁ to C₂₀ cycloalkyl, C₆ to C₂₀ aryl,acetal, ketal, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine,chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl,hydrocarbylsulfonyl, hydrocarbylcarbonyl or cyclic ether; each R isindividually selected from the group consisting of hydrogen, ethenyl,propenyl, acryloyl, methacryloyl and an organic radical with a terminalethenyl, propenyl, acryloyl, or methacryloyl group; each R″ isindividually selected from the group consisting of hydrogen, linear orbranched alkyl, cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy,aryloxy, formyl, ester, fluorine, chlorine, bromine, perhaloalkyl,hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarbylcarbonyl, cyclicether, ethenyl, propenyl, and an organic radical with a terminal ethenylor propenyl group; provided at least one R represents ethenyl, propenyl,acryloyl, methacryloyl or the organic radical with a terminal ethenyl,propenyl, acryloyl, or methacryloyl group or at least one R″ representsethenyl, propenyl, or the organic radical with a terminal ethenyl orpropenyl group, at atmospheric pressure and a temperature between 20° C.and 150° C. for 1 to 100 hours to produce the polymeric composition. 6.A compound of claim 5, Formula I, wherein a=2, b=0, R is primary orsecondary alkyl located ortho to the oxygen bonded to Ar, wherein y≧1,and wherein at least one R″ is primary or secondary alkyl group and islocated at the ortho position of the oxygen bonded to the binaphthalenegroup, or a compound of claim 5, Formula II wherein a=2, b=0, R isprimary or secondary alkyl located ortho to the oxygen bonded to Ar,wherein x≧1 and wherein at least one R″ is primary or secondary alkylgroup and is located at the ortho positions of the oxygen bonded to thebiphenylene group.
 7. The method of claim 5 wherein the initiator is afree radical initiator.
 8. A polymeric, phosphorus-containingcomposition made by the process of claim
 5. 9. A method for making apolymeric composition by heating, in the presence of an initiator, acomposition comprising at least one compound of Formula III or at leastone compound of Formula IV:

wherein: x=0 to 4; y=0 to 2; each R′ is individually selected from thegroup consisting of hydrogen or an alkali metal or an alkaline earthmetal or a hydroxyl protective group selected from the group consistingof alkyl, alkoxyalkyl, carbonylalkyl, and a crown ether formed by takingboth R′ groups together; each R″ is individually selected from the groupconsisting of hydrogen, linear or branched alkyl, cycloalkyl, acetal,ketal, aryl, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine,chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl,hydrocarbylsulfonyl, hydrocarboylcarbonyl, cyclic ether, ethenyl,propenyl, and an organic radical with a terminal ethenyl or propenylgroup; provided at least one R″ is ethenyl, propenyl, or the organicradical with a terminal ethenyl or propenyl group.
 10. A compound ofclaim 9, Formula I, wherein a=2, b=0, R is primary or secondary alkyllocated ortho to the oxygen bonded to Ar, wherein y≧1 and wherein atleast one R″ is primary or secondary alkyl group and is located at theortho position of the oxygen bonded to the binaphthalene group, or acompound of claim 1, Formula II wherein a=2, b=0, R is primary orsecondary alkyl located ortho to the oxygen bonded to Ar, wherein x≧1and wherein at least one R″ is primary or secondary alkyl group and islocated at the ortho positions of the oxygen bonded to the biphenylenegroup.
 11. The method of claim 9 wherein the initiator is a free radicalinitiator.
 12. A polymeric composition made by the method of claim 9.13. A process for making a polymeric, phosphorus-containing compositionby: (1) heating, in the presence of an initiator, a compositioncomprising at least one compound of Formula III and/or at least onecompound of Formula IV:

wherein: x=0 to 4; y=0 to 2; each R′ is individually selected from thegroup consisting of hydrogen or an alkali metal or an alkaline earthmetal or a hydroxyl protective group selected from the group consistingof alkyl, alkoxyalkyl, carbonylalkyl, and a crown ether formed by takingboth R′ groups together; each R″ is individually selected from the groupconsisting of hydrogen, linear or branched alkyl, cycloalkyl, acetal,ketal, aryl, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine,chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl,hydrocarbylsulfonyl, hydrocarboylcarbonyl, cyclic ether, ethenyl,propenyl, and an organic radical with a terminal ethenyl or propenylgroup; provided at least one R″ is ethenyl, propenyl, or the organicradical with a terminal ethenyl or propenyl group and (2) if R′ is ahydroxyl protective group, converting R′ to H or an alkali metal oralkaline earth metal and, (3) phosphonylating the product of step (1) ifR′ is other than a hydroxyl protective group, or the product of steps(1) and (2) if R′ is a hydroxyl protective group, with trivalentphosphorus of a diaryloxyphosphite unit, —P(—O—Ar)₂, a diarylphosphineunit, —P(Ar)₂, or an aryl,aryloxyphosphinite unit, —P(Ar)(—O—Ar), ormixture thereof, where each Ar is individually selected from the groupconsisting of phenyl, substituted phenyl, naphthyl, and substitutednaphthyl, provided that the two Ar groups that are directly orindirectly bonded to the same phosphorus atom may be linked to eachother by a linking unit selected from the group consisting of directbond, alkylidene, secondary or tertiary amine, oxygen, sulfide, sulfone,and sulfoxide.
 14. A compound of claim 13, wherein the trivalentphosphorus is a diaryloxyphosphite unit, —P(—O—Ar)₂, and the compound ofFormula III, wherein a=2, b=0, the Ar group contains a primary orsecondary alkyl located ortho to the oxygen bonded to Ar, wherein y≧1and wherein at least one R″ is primary or secondary alkyl group and islocated at the ortho position of the oxygen bonded to the binaphthalenegroup, or a compound of claim 13, Formula IV wherein a=2, b=0, the Argroup contains a primary or secondary alkyl located ortho to the oxygenbonded to Ar, wherein x≧1 and wherein at least one R″ is primary orsecondary alkyl group and is located at the ortho positions of theoxygen bonded to the biphenylene group.
 15. The method of claim 13wherein the initiator is a free radical initiator.
 16. A polymericcomposition made by the method of claim
 13. 17. A method to produce apolymeric, phosphorus-containing composition by heating aphosphorochloridite containing at least one acrylate or methyl acrylategroup in the presence of an initiator to produce a polymer containingphosphorochloridite, and further reacting this polymer with acomposition comprising at least one compound of Formula III and/orFormula IV:

wherein: x=0 to 4; y=0 to 2; each R′ is individually selected from thegroup consisting of hydrogen or an alkali metal or an alkaline earthmetal or a hydroxyl protective group selected from the group consistingof alkyl, alkoxyalkyl, carbonylalkyl, and a crown ether formed by takingboth R′ groups together, with the provision that if R′ is protected, theprotecting group must be removed before reacting the compound of FormulaIII and/or Formula IV with the polymer containing phosphorochloridite;each R″ is individually selected from the group consisting of hydrogen,linear or branched alkyl, cycloalkyl, acetal, ketal, aryl, alkoxy,cycloalkoxy, aryloxy, formyl, ester, fluorine, chlorine, bromine,perhaloalkyl, hydrocarbylsulfinyl, hydrocarbylsulfonyl,hydrocarboylcarbonyl, cyclic ether, ethenyl, propenyl, and an organicradical with a terminal ethenyl or propenyl group; provided at least oneR″ is ethenyl, propenyl, or the organic radical with a terminal ethenylor propenyl group.
 18. A compound of claim 17, Formula III, wherein a=2,b=0, R is primary or secondary alkyl located ortho to the oxygen bondedto Ar, wherein y≧1, and wherein at least one R″ is primary or secondaryalkyl group and is located at the ortho position of the oxygen bonded tothe binaphthalene group, or a compound of claim 17, Formula IV, whereina=2, b=0, R is primary or secondary alkyl located ortho to the oxygenbonded to Ar, wherein x≧1 and wherein at least one R″ is primary orsecondary alkyl group and is located at the ortho positions of theoxygen bonded to the biphenylene group.
 19. The method of claim 17 wherethe initiator is a free radical initiator.
 20. A polymeric compositionmade by the method of claim
 17. 21. A catalyst composition comprising(1) at least one monomeric, phosphorus-containing composition of claim 1and at least one Group VIII metal, or (2) at least one polymeric,phosphorus-containing composition of claim 8, and at least one GroupVIII metal, or (3) at least one polymeric, phosphorus-containingcomposition of claim 12, claim 16, or claim 20 and at least one GroupVIII metal.
 22. The catalyst composition of claim 21 wherein the GroupVIII metal is nickel, palladium, or cobalt.
 23. The catalyst compositionof claim 21 wherein the Group VIII metal is rhodium, iridium orplatinum.
 24. The catalyst composition of claim 21 wherein the GroupVIII metal is nickel.
 25. The catalyst composition of claim 22 or 24further comprising a Lewis acid.
 26. The catalyst composition of claim25 wherein the Lewis acid is selected from the group consisting ofZnBr₂, Znl₂, ZnCl₂, ZnSO₄, CuCl₂, CuCl, Cu(O₃SCF₃)₂, COCl₂, Col₂, Fel₂,FeCl₃, FeCl₂, FeCl₂(THF)₂, TiCl₄(THF)₂, TiCl₂, ClTi(OiPr)₂, MnCl₂,ScCl₃, AlCl₃, (C₈H₁₇)AlCl₂, (C₈H₁₇)₂AlCl, (iso-C₄H₉)₂AlCl, Ph₂AlCl,PhAlCl₂, ReCl₅, ZrCl₄, NbCl₅, VCl₃, CrCl₂, MoCl₅, YCl₃, CdCl₂, LaCl₃,Er(O₃SCF₃)₃, Yb(O₂CCF₃)₃, SmCl₃, B(C₆H₅)₃, (C₆H₅)₃SnX, where X═CF₃SO₃,CH₃C₆H₅SO₃, or (C₆H₅)₃BCN and TaCl₅.
 27. The catalyst composition ofclaim 26 wherein the Lewis acid is zinc chloride or iron chloride.
 28. Ahydroformylation process comprising contacting an unsaturated organiccompound with CO and H₂ in the presence of a catalyst compositioncomprising (1) at least one monomeric, phosphorus-containing compositionof claim 1 and at least one Group VIII metal, or (2) at least onepolymeric, phosphorus-containing composition of claim 8, and at leastone Group VIII metal, or (3) at least one polymeric,phosphorus-containing composition of claim 12, claim 16, or claim 20 andat least one Group VIII metal.
 29. The hydroformylation process of claim28 wherein the Group VIII metal is rhodium, iridium or platinum.
 30. Thehydroformylation process of claim 29 wherein the unsaturated organiccompound is selected from the group consisting of 3-pentenenitrile,3-pentenoic acid, 3-pentenal, allyl alcohol, and alkyl 3-pentenoate ormixture thereof.
 31. The hydroformylation process of claim 30 whereinthe unsaturated organic compound contains less than 100 ppm peroxidesand the Group VIII metal is rhodium.
 32. A hydrocyanation processcomprising contacting an unsaturated organic compound with HCN in thepresence of a catalyst composition comprising (1) at least onemonomeric, phosphorus-containing composition of claim 1 and at least oneGroup VIII metal, or (2) at least one polymeric, phosphorus-containingcomposition of claim 8, and at least one Group VIII metal, or (3) atleast one polymeric, phosphorus-containing composition of claim 12,claim 16, or claim 20 and at least one Group VIII metal, and optionallya Lewis acid.
 33. The hydrocyanation process of claim 32 wherein theLewis acid is selected from the group consisting of ZnBr₂, Znl₂, ZnCl₂,ZnSO₄, CuCl₂, CuCl, Cu(O₃SCF₃)₂, CoCl₂, Col₂, Fel₂, FeCl₃, FeCl₂,FeCl₂(THF)₂, TiCl₄(THF)₂, TiCl₂, ClTi(OiPr)₂, MnCl₂, ScCl₃, AlCl₃,(C₈H₁₇)AlCl₂, (C₈H₁₇)₂AlCl, (iso-C₄H₉)₂AlCl, Ph₂AlCl, PhAlCl₂, ReCl₅,ZrCl₄, NbCl₅, VCl₃, CrCl₂, MoCl₅, YCl₃, CdCl₂, LaCl₃, Er(O₃SCF₃)₃,Yb(O₂CCF₃)₃, SmCl₃, B(C₆H₅)₃, and TaCl₅.
 34. The hydrocyanation processof claim 33 wherein the Lewis acid is zinc chloride or iron chloride.35. The hydrocyanation process of claim 34 wherein the Group VIII metalis nickel, palladium or cobalt.
 36. The hydrocyanation process of claim35 wherein the Group VIII metal is nickel.
 37. The hydrocyanationprocess of claim 36 wherein the unsaturated organic compound is3-pentenenitrile or 4-pentenenitrile or mixture thereof.
 38. Thehydrocyanation process of claim 37 wherein the HCN contains less than 20ppm sulfur dioxide, less than 40 ppm sulfuric acid, less than 20 ppmcyanogen, less than 10 ppm epoxide, less than 20 ppm acrylonitrile, andless than 100 ppm peroxides, and the pentenenitriles contain less than100 ppm peroxides.
 39. The hydrocyanation process of claim 32 whereinthe Group VIII metal is nickel, palladium or cobalt and the unsaturatedorganic compound is 1,3-butadiene.
 40. The hydrocyanation process ofclaim 39 wherein the Group VIII metal is nickel.
 41. The hydrocyanationprocess of claim 40 wherein the HCN contains less than 20 ppm sulfurdioxide, less than 40 ppm sulfuric acid, less than 20 ppm cyanogen, lessthan 10 ppm epoxide, less than 20 ppm acrylonitrile, and less than 100ppm peroxides, and the 1,3-butadiene contains less than 5 ppm t-butylcatechol, less than 500 ppm vinylcyclohexene, and less than 100 ppmperoxides.
 42. An isomerization process comprising reacting anunsaturated organic nitrile compound in the presence of a catalystcomposition comprising (1) at least one monomeric, phosphorus-containingcomposition of claim 1 and at least one Group VIII metal, or (2) atleast one polymeric, phosphorus-containing composition of claim 8, andat least one Group VIII metal, or (3) at least one polymeric,phosphorus-containing composition of claim 12, claim 16, or claim 20 andat least one Group VIII metal.
 43. The isomerization process of claim 42wherein the Group VIII metal is nickel, palladium or cobalt.
 44. Theisomerization process of claim 43 wherein the unsaturated organicnitrile compound is 2-methyl-3-butenenitrile and the Group VIII metal isnickel.
 45. The isomerization process of claim 44 wherein the2-methyl-3-butenenitrile contains less than 100 ppm peroxides.